Complexed surfactant system

ABSTRACT

The present invention relates to a mixed surfactant system, and particularly to a mixed surfactant system which comprises an anionic surfactant and a compound comprising at least one kind of non-ionic group or cationic group, and which thus increases cleaning power of the anionic surfactant, increases stability to hard water, lowers surface tension and cmc, and can control initial foamability and foam stability by the mixing ratio of the non-ionic surfactant and the cationic surfactant that can be added together, and that is therefore very useful for a detergent of solid, liquid, gel, or paste types.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to a mixed surfactant system showingsuperior properties by controlling interfacial properties such ascleaning power, foaming property, stability to hard water, surfacetension, etc.

(b) Description of the Related Art

It is known that all surfactants including anionic, cationic, non-ionic,and amphoteric surfactants exist as single molecules below a criticalmicelle concentration (hereinafter referred to as ‘cmc’), and they formmicelles when reaching a cmc to show unique surface active propertiesaccording to each compound.

However, since surface active properties shown by one kind of surfactantcannot be superior in every respect, studies for overcoming this areunder progress. First, studies on mixing surfactants having the sameionicity were undertaken, and then many studies on mixing ionicsurfactants and non-ionic surfactants were done. However, few studiesfor mixing surfactants with different ionicities have been performedthus far, because it has been known that compounds are neutralized whensurfactants with different ionicities are mixed and they do not dissolvein water and therefore they form precipitates.

Generally, if anionic and cationic surfactants are simultaneouslydissolved in an aqueous solution, they can exist in three forms. First,an anionic surfactant and a cationic surfactant independently exist asfree single bodies; second, an anionic surfactant and a cationicsurfactant form a complex to become a precipitate; and third, an anionicsurfactant and a cationic surfactant form a mixed micelle and aredissolved in the aqueous solution. The complex formed by binding of theanionic and cationic surfactants is called a pseudo-nonionic complexsurfactant, and it is known that such a neutral complex can have itssolubility increased in water as it has more hydrophilic groups thandoes a nonionic surfactant. Therefore, these three forms of surfactantsare largely influenced by the structure and concentration of the anionicand cationic surfactants. It is known that in order to preventprecipitation, which may occur in the case of an anionic surfactant anda cationic surfactant being mixed to form a mixed surfactant system, andto improve phase stability and physical properties, non-ionicsurfactants are mixed. Particularly, it has been reported that in thecase of non-ionic surfactants in which an amine oxide, an ethyleneoxide, or a propylene oxide as a hydrophilic group are added, superioreffects in terms of various surface active effects (for examplesolubility, cleaning power, emulsifying power, dispersing power,lowering surface tension power, low cmc, etc.) can be obtained, andphase stability of the mixed surfactant can be improved (Surfactantscience series vol. 46, mixed surfactant systems).

Recently, patents with the object of improving effects of products bymixing an anionic surfactant, a cationic surfactant, and a non-ionicsurfactant in a specific ratio have been published.

U.S. Pat. No. 5,798,329 disclosed a method for prescribing a detergentshowing superior effects in concentrated or common form. The superioreffects mean superior foaming property, and satisfactory cleaning powerand antibacterial power. According to this method, approximately 1˜40 wt% of one or more kinds of anionic surfactants selected fromalkylethercarboxylates or alkylethersulfates; approximately 3˜50 wt % ofone or more kinds of non-ionic surfactants selected from alcoholalkoxylates, alkylphenol ethoxylates, alkylpolyglycosides, amine oxides,and alkanolamides; and approximately 1˜25 wt % of cationic surfactantsselected from one or more kinds of compounds with quaternary ammoniumcompounds were used in order to improve cleaning power. The cationicsurfactant used in this method was a generally-used quaternary ammoniumcompound, and the non-ionic surfactant was a presently marketed commonsurfactant.

U.S. Pat. No. 4,576,729 disclosed a method for preparing a liquiddetergent with superior phase stability by mixing non-ionic, anionic,and cationic surfactants in a ratio of 2:4:1˜3.5:5:1.

U.S. Pat. No. 5,230,823 described a method for mixing anionic andnon-ionic surfactants for a gel type dishwashing detergent, andaccording to this method, a quaternary ammonium surfactant of a specifictype is included in the composition as a foam enhancer.

However, although these methods asserted that cleaning power issuperior, they do not mention other physical properties such asstability to hard water, foaming property, surface tension, etc. Also,the non-ionic surfactants used in the above methods are not compoundsprepared in order to improve specific effects, but rather methodscombining commonly used compounds to obtain a functional mixing ratio.

In addition, Korean Patent Laid Open-Publication No. 2000-10944disclosed a detergent composition for washing, comprising a dimethylhydroxyethyl quaternary ammonium surfactant comprising C12˜C14 alkylgroups combined with a polyamine filth-dispersing agent in order toincrease fabric washing power. However, the quaternary ammoniumsurfactant used in this method fixes the length of the alkyl groups asC12˜C14, and this method describes the function of cationic surfactantsfor improving effects of the polyamine to simply improve filth-removingpower when washing synthetic fabrics (for example, polyester) and adetergent composition comprising the same.

In addition, U.S. Pat. No. 6,022,844 clarified that a cationicsurfactant was added to a conventional detergent prescription to improveoil-removing power and to simultaneously maintain a scent for a longtime and prevent color bleeding. However, this method only describesmixing about 0.1˜3% of the cationic surfactant, and it did not apply anovel compound for controlling physical properties.

SUMMARY OF THE INVENTION

The present invention is made in consideration of the problems of theprior art, and it is an object of the present invention to provide acompound with a novel structure that can improve physical properties ofan anionic surfactant or mixed system of anionic and cationicsurfactants.

It is another object of the present invention to provide a mixedsurfactant system using the compound to show superior effects comparedto using an anionic surfactant alone.

It is another object of the present invention to provide a surfactantsystem with superior surface active properties such as cleaning power,initial foaming property, stability to hard water, surface tension, cmc,moisturizing power, foam stability, etc.

It is another object of the present invention to provide a detergentcomposition of a solid, liquid, gel, or paste types comprising thesurfactant system, to show effects superior to those of the conventionalproducts.

In order to achieve these objects, the present invention provides asurfactant system comprising

-   -   a) an anionic surfactant;    -   b) a cationic compound represented by the following Chemical        Formula 1; and    -   c) a non-ionic surfactant:    -   wherein    -   R₁, R₂, R₃, and R₄ are independently or simultaneously C1˜C20        saturated or unsaturated chain groups, benzyl groups,        hydroxylethyl groups, or hydroxy ethyl groups to which 1 to 20        ethylene oxide groups or propylene oxide groups are attached;        and    -   X is halogen atom, a sulfate group, or an acetate group.

The present invention also provides a surfactant system comprising

-   -   a) an anionic surfactant; and    -   b) a cationic compound represented by the following Chemical        Formula 2:    -   wherein    -   R₁, R₂, R₃, and R₅ are independently or simultaneously C1˜C20        saturated or unsaturated chain groups, benzyl groups,        hydroxylethyl groups, or hydroxylethyl groups to which 1 to 20        ethylene oxide groups or propylene oxide groups are attached; R₄        is a C1˜C20 alkyl group, an alkyl group to which 1˜10 ethylene        oxide groups or propylene oxide groups are attached, or an alkyl        group to which 1 or more hydroxyl groups are bound; n is an        integer of 1 to 20; and X is halogen atom, a sulfate group, or        an acetate group.

The present invention also provides a surfactant system comprising

-   -   a) an anionic surfactant; and    -   b) a compound represented by the following Chemical Formula 4:    -   wherein    -   R₁, R₂, R₃, and R₄ are independently or simultaneously C1˜20        saturated or unsaturated chain groups, benzyl groups, hydroxy        ethyl groups, or hydroxy ethyl groups to which 1˜20 ethylene        oxide groups or propylene oxide groups are attached; R₅ is a        C1˜20 alkyl group, an alkyl group to which 1˜20 ethylene oxide        or propylene oxide groups are attached, an alkyl group to which        1 or more hydroxyl groups are bound, an alkyl group comprising        at least one double bond, or an alkyl group comprising at least        one ether group; A₁ and A₂ are independently or simultaneously        C1˜20 saturated or unsaturated chain groups, benzyl groups,        hydroxy ethyl groups, hydroxylethyl groups to which 1˜20        ethylene oxide or propylene oxide groups are attached, or oxygen        anions (O—); n is an integer of 0 to 20; and X is a halogen        atom, a sulfate group, a methylsulfate group, or an acetate        group.

The present invention also provides a surfactant system comprising;

-   -   a) an anionic surfactant;    -   b) a compound represented by the above Chemical Formula 4; and    -   c) a non-ionic surfactant, a cationic surfactant, or a mixture        thereof.

The present invention also provides a detergent composition of a solid,liquid, gel, or paste types comprising the above surfactant systems.

DETAILED DESCRIPTION AND THE PREFERRED EMBODIMENTS

The present invention will now be explained in detail.

The present inventors, in order to solve the problems of the prior artand show superior surface active properties in every respect (forexample, cleaning power, foaming property, stability to hard water,surface tension, cmc, moisturizing power, foam stability, etc.), havebound a plurality of hydrophilic groups to a neutral complex produced inan appropriate concentration so as to not form a precipitate to increasesolubility to water, thereby preventing precipitation, and consequentlydeveloped a compound represented by the above Chemical Formula 1, 2, or4 that can control physical properties of an anionic surfactant.

Accordingly, the present invention provides a surfactant systemcomprising a compound represented by the above Chemical Formula 1, 2, or4 in a specific ratio so as to increase physical properties of theconventional anionic surfactant and thus show superior effects.

According to the present invention, the compound of the above ChemicalFormula 1, 2, or 4 is used to control desired physical properties, andeven if a small amount thereof is mixed, superior effects can beobtained. Also, the present invention, in order to further improvefilth-removing power, prepares a cationic compound of Chemical Formula 4of a Gemini structure to apply it as an additive, thereby improving orcontrolling desired physical properties.

Structures similar to that of the cationic compound used in the presentinvention have been announced by R. Zana (Journal of Colloid andInterface Science, 1998, 199, 169) and R. Rosen (Journal of Colloid andInterface Science, 1996, 179, 261; Journal of Colloid and InterfaceScience, 1996, 179, 454). However, compounds announced in theaforementioned literature were synthesized as novel cationic surfactantsand unique physical properties thereof were measured, and studiesregarding a surfactant system mixing anionic surfactants to showsuperior surface active effects, the object of the present invention,have not been previously undertaken. Moreover, since the compoundsannounced in the above literature have small hydrophilic groups inmolecules, they are very likely to become precipitates when mixed withan anionic surfactant as in the present invention.

The present invention, in order to solve the problems of the compoundsannounced in the above literature, uses a compound of Chemical Formula 1wherein a hydroxyl group is introduced in a molecule, or a compound ofChemical Formula 2 wherein one or more kinds of cationic groups and ahydroxyl group are introduced in a molecule, to improve solubility ofthe produced neutral complex thereby showing superior surface activeproperties.

In addition, the present invention uses a compound of Chemical Formula 1wherein one or more kinds of cationic groups or an amine oxide group anda hydrophilic group, i.e., a hydroxyl group, ethylene oxide (EO), orpropylene oxide (PO), are introduced in a molecule to improve solubilityof the produced neutral complex, thereby showing superior surface activeeffects.

Specifically, according to the present invention, the compoundrepresented by the above Chemical Formula 1, 2, or 4 increases cleaningpower of an anionic surfactant alone, or an anionic surfactant and anon-ionic surfactant, a cationic surfactant, or a mixture thereof, anddecreases foam stability while maintaining initial foam, and improvesstability to hard water and lowers surface tension and cmc.

The surfactant system of the present invention will now be explained inmore detail.

The surfactant system of the present invention comprises an anionicsurfactant, a cationic compound of the above Chemical Formula 1, and anon-ionic surfactant, in a specific ratio.

In the surfactant system of the present invention, the mixing ratio ofthe anionic surfactant, the cationic compound of Chemical Formula 1, andthe non-ionic surfactant is preferably 1:0.001:0.001˜1:1:1. If the moleratio of the anionic surfactant and the cationic compound of ChemicalFormula 1 is less than 1:0.001, little change in physical properties ofa mixed surfactant system accompanied by mixing the cationic compoundappears, and if it exceeds 1:1, it is uneconomical.

In the surfactant system of the present invention, the cationic compoundof Chemical Formula 1 is quaternary ammonium compound comprising atleast one kind of hydrophilic group in its structure. The cationiccompound represented by Chemical Formula 1 of the above structureincreases solubility of a neutral compound produced when binding withthe anionic surfactant in water to show superior effects.

The cationic compound of Chemical Formula 1 can be prepared byheat-reacting a tertiary amine of a structure corresponding to theobject of the present invention with an alkyl halide under basicconditions to cause quaternarization.

The cationic compound of Chemical Formula 1 thus obtained can beprepared as a mono-type compound comprising one kind of quaternaryammonium group as a representative cationic group, or into a compoundwherein an ethylene oxide (EO) group is added to a hydroxyl group of themono-type compound as a non-ionic hydrophilic group.

In addition, the surfactant system of the present invention comprises ananionic surfactant and a cationic compound of Chemical Formula 2 in aspecific ratio.

In this surfactant system of the present invention, the mixing ratio ofthe anionic surfactant and the cationic compound of Chemical Formula 2is preferably 1:0.0001˜1:0.5. If the mole ratio of the anionicsurfactant and the cationic compound of the above Chemical Formula 2 isless than 1:0.0001, little change in physical properties of a mixedsurfactant system accompanied by mixing the cationic compound appears,and if it exceeds 1:0.5, it is uneconomical.

In the surfactant system of the present invention, the cationic compoundof Chemical Formula 2 is in the form of quaternary ammonium comprisingat least one kind of cationic group and hydrophilic group in itsstructure. The cationic compound of Chemical Formula 2 of the abovestructure can increase solubility of a neutral compound produced whenbinding with an anionic surfactant in water to show superior effects.

In the present invention, the cationic compound of Chemical Formula 2,which is mixed with the anionic surfactant in order to show moresuperior effects, can be prepared by the following two methods.

First, the cationic compound of Chemical Formula 1 can be prepared by i)reacting a secondary amine with a linker represented by the followingChemical Formula 3 under alkaline conditions to prepare a tertiaryamine; and ii) reacting the tertiary amine with various kinds of alkylhalides to cause quaternarization.

Second, the cationic compound of Chemical Formula 1 can be prepared byi) reacting a secondary amine with various kinds of alkyl halides underalkaline conditions to prepare a tertiary amine; and ii) binding alinker represented by Chemical Formula 3 to the tertiary amine obtainedin step i) to cause quaternarization.X—(CH_(n))n-X  [Chemical Formula 3]wherein n is an integer of 1 to 20, and X is a halogen atom, a sulfategroup, or an acetate group.

The secondary amine corresponding to the object of the present inventionis heated with various kinds of alkyl groups under alkaline conditionsto prepare a tertiary amine, and then it is reacted with a compound ofChemical Formula 3 functioning as a linker to cause quaternarization,one example of which is as shown in the following Equation 1.

-   -   wherein R is a C1˜20 saturated or unsaturated chain group, a        benzyl group, a hydroxy ethyl group, or 1 to 20 hydroxy ethyl        groups to which ethylene oxide or propylene oxide groups are        attached; n is an integer of 1 to 20; and X is a halogen atom, a        sulfate group, or an acetate group.

Alternatively, a secondary amine corresponding to the object of thepresent invention is reacted with a compound of Chemical Formula 3 tosynthesize a tertiary amine under alkaline conditions, and then it isreacted with various kinds of alkyl groups to cause quaternarization,one example of which is as shown in the following Equation 2.

-   -   wherein R is a C1˜20 saturated or unsaturated chain group, a        benzyl group, a hydroxy ethyl group, or a hydroxy ethyl group to        which 1 to 20 ethylene oxide or propylene oxide groups are        attached; n is an integer of 1 to 20; and X is a halogen atom, a        sulfate group, or an acetate group.

Among the cationic compounds of Chemical Formula 2, bis-forms can beprepared through the reaction pathways of the above Equations 1 or 2.

In addition, the cationic compound comprising 3 or more cationic groupsin one molecule can be obtained by reacting an equal number of moles ofa secondary amine and epichlorohydrin in an alcohol solvent tosynthesize an intermediate, and then polymerizing the intermediate. Thepolymerization degree of the cationic compound can be controlled bycontrolling time and temperature of polymerization. The synthesispathway of the oligomer-type cationic compound is as shown in thefollowing Equation 3.

In the present invention, a cationic compound can be easily synthesizedby selecting an appropriate method according to a desired compound. Thesynthesize compound can be confirmed using NMR and MASS analysis.

The cationic compound of Chemical Formula 1 is preferably selected froma group consisting of 1,6-[2(N-dimethylamino)ethanol]hexane,1,6-[2-(N,N-ethylmethyl amino)ethano]hexane, 1,6-[2-(N,N-butylmethylamino)ethanol]hexane, 1,6-[2-(N,N-methyloctyl amino)ethanol]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol]hexane, 1,8-[2-(N-dimethylamino)ethanol]octane, 1,8-[2-(N,N-ethylmethyl amino)ethanol]octane,1,8-[2-(N,N-butylmethyl amino)ethanol]octane,1,8-[2-(N,N-methyloctylamino)ethanol]octane, 1,8-[2-(N,N-dodecylmethylamino)ethano]octane, 1,6-[2-(N-dimethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-ethylmethyl amino)ethanol(EO)₂]hexane,1,6-[2-(N,N-methyloctyl amino)ethanol(EO)₂]hexane,1,6-[2-(N,N-methyloctyl amino)ethanol(EO)₂]hexane,1,6-[2-(N,N-dodecylmethyl amino)ethanol(EO)₂]hexane, 1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane, 1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₄]hexane, 1,6-[2-(N,N-butylmethylamino)ethanol(EO)₄]hexane, 1,6-[2-(N,N-methyloctylamino)ethanol(EO)₄]hexane, 1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]hexane, 1,8-[2-(N-dimethyl amino)ethanol(EO)₂]octane,1,8-[2-(N,N-ethylmethyl amino)ethanol(EO)₂]octane,1,8-[2-(N,N-butylmethyl amino)ethanol(EO)₄]octane,1,8-[2-(N,N-methyloctyl amino)ethanol(EO)₄]octane,1,8-[2-(N,N-dodecylmethyl amino)ethanol(EO)₄]octane, 1,8-[2-(N-dimethylamino)ethanol(EO)₄]octane, 1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₄]octane, 1,8-[2-(N,N-butylmethylamino)Ethanol(EO)₄]octane, 1,8-[2-(N,N-methyloctylamino)ethanol(EO)₄]octane, 1,8-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]octane, 1,6-[2-(N-dimethyl amino)ethanol(PO)₂]hexane,1,6-[2-(N,N-ethylmethyl amino)ethanol(PO)₂]hexane,1,6-[2-(N,N-methyloctyl amino)ethanol(PO)₂]hexane,1,6-[2-(N,N-dodecylmethyl amino)ethanol(PO)₂]hexane,1,6-[2-(N-dimethylamino) Ethanol(PO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-butylmethyl amino)ethanol(PO)₄]hexane,1,6-[2-(N,N-methyloctyl amino)ethanol(PO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)Ethanol(PO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-butylmethylamino) Ethanol(PO)₂]octane,1,8-[2-(N,N-butylmethyl amino)ethanol(PO)₂]octane,1,8-[2-(N,N-methyloctylamino) Ethanol (PO)₂]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N-dimethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₄]octane, and1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]octane.

In addition, the surfactant system of the present invention comprises ananionic surfactant and a compound of the above Chemical Formula 4.

The mixing ratio of the anionic surfactant and the compound of ChemicalFormula 4 is preferably 1:0.0001˜1:1.0 by mole ratio. If the mole ratioof the anionic surfactant and the compound of Chemical Formula 4 is lessthan 1:0.0001, little change in physical properties of a mixedsurfactant system accompanied by mixing a non-ionic compound appears,and if exceeding 1:1.0, it is uneconomical.

Also, the surfactant system of the present invention may furthercomprise a non-ionic surfactant, a cationic surfactant, or a mixturethereof in addition to the mixed system of the anionic surfactant andthe compound of Chemical Formula 4 to form a mixed surfactant systemshowing more superior effects.

In the case of a mixed system of an anionic surfactant, a compound ofChemical Formula 4, and a non-ionic surfactant, the mixing ratio thereofis preferably 1:0.0001:0.0001˜1:1.0:0.5 by mole ratio.

Also, in the case of a mixed system of an anionic surfactant, a compoundof Chemical Formula 4, and a cationic surfactant, the mixing ratiothereof is preferably 1:0.0001:0.0001˜1:1.0:0.5 by mole ratio.

Also, in the case of a mixed system of an anionic surfactant, a compoundof Chemical Formula 4, a non-ionic surfactant, and a cationicsurfactant, the mixing ratio thereof. Is preferably1:0.0001:0.0001:0.0001˜1:1.0:0.5:0.5.

In addition, in the surfactant system of the present invention, thecompound of Chemical Formula 4 comprises a cationic group or an anionicgroup in its molecular structure, and the compound comprises at leastone hydrophilic group. The compound of Chemical Formula 4 of the abovestructure, if binding with an anionic surfactant, increases solubilityof the produced mixture in water to show superior effects.

In Chemical Formula 4, when A₁ and A₂ are oxygen anions, a cation ofnitrogen and an anion of oxygen charge-offset each other to showcharacteristics of a nonionic compound. Also, in Chemical Formula 1,when A₁ and A₂ are independently or simultaneously C1˜20 saturated orunsaturated chain groups, benzyl groups, hydroxy ethyl groups, orhydroxy ethyl groups to which 1˜20 ethylene oxide or propylene oxidegroups are attached, the compound shows characteristics of an cationiccompound.

In the compound of Chemical Formula 4, when an oxygen anion is bound toA₁ and A₂, specifically when the compound is a non-ionic compoundcomprising an amine oxide group, it can be prepared by the followingmethods.

First, the non-ionic compound of the above Chemical Formula 4 can beprepared by a) reacting a secondary amine with a linker of the followingChemical Formula 5 under alkaline conditions to prepare a tertiaryamine; and b) reacting the obtained tertiary amine with peroxide (H₂O₂).

-   -   wherein n is an integer of 1 to 20; X is a halogen atom; R₅ is        hydrogen, or a C1˜20 alkyl or allyl group comprising at least        one double bond, hydroxyl group, or ether group.

A secondary amine corresponding to the object of the present inventionand the compound of the above Chemical Formula 4 are reacted tosynthesize a tertiary amine under alkaline conditions, and then it isreacted with peroxide to prepare amine oxide, one example of which is asshown in the following Equation 4:

-   -   wherein R is a C1˜20 saturated or unsaturated chain group,        benzyl group, hydroxy ethyl group, or hydroxy ethyl group to        which 1 to 20 ethylene oxide or propylene oxide groups are        attached; n is an integer of 1 to 20; X′ is a halogen atom; R₅        is hydrogen, or a C1-20 alkyl or allyl group comprising at least        one double bond, hydroxyl group, or ether group.

Among the non-ionic compounds of Chemical Formula 4, bis-forms can beprepared through the pathway of Equation 4.

Also, a compound of Chemical Formula 4 comprising 3 or more amine oxidegroups in one molecule can be prepared by the following methods.

It can be prepared by reacting an equal number of moles of a primaryamine and epichlorohydrin in an alcohol solvent to synthesize asecondary amine intermediate, and then polymerizing the intermediate toa tertiary amine and reacting it with peroxide. The polymerizationdegree of the intermediate can be controlled by controlling time andtemperature of polymerization when synthesizing the tertiary amine. Oneexample of the synthesis pathway of the non-ionic compound of sucholigomer form is as shown in the following Equation 5.

-   -   wherein R₁, n, and X are as defined in the above.

The present invention can select an appropriate synthesis methodaccording to a desired compound to easily synthesize a non-ioniccompound. The synthesized compound can be confirmed using NMR and MASSanalysis.

Among the compound of Chemical Formula 4 prepared by the above method, anon-ionic compound is preferably selected from a group consisting ofN,N,N-dimethyllauryl amine oxide; N,N,N-ethylmethyllauryl amine oxide;N,N,N-dimethyldodecyl amine oxide; N,N,N-butylmethyllauryl amine oxide;N,N,N-dimethylhexadecyl amine oxide; N,N,N-dibutyllauryl amine oxide;N,N,N-(2-hydroxyethyllaurylmethyl)amine oxide;N,N,N-(di-2-hydroxyethyllauryl)amine oxide; N,N,N-(2-hydroxyethyllaurylbutyl)amine oxide; N,N,N-(2-hydroxy(EO)₅ethyllaurylmethyl)amine oxide;N,N,N-(2-hydroxyethyl(PO)₅laurylmethyl)amine oxide;N,N,N-(2-hydroxyethyl(EO)₅(PO)₅laurylmethyl)amine oxide;N,N,N-(2-hydrxoyethyl(EO)₁₀laurylmethyl)amine oxide;N,N,N-(2-hydrxoyethyl(EO)₁₅laurylmethyl)amine oxide;1,6-(N,N-butylmethylaminooctyl)hexane;1,6-(N,N-butylmethylaminooctyl)dipropylether;1,6-(N,N-butylmethylaminooctyl)-3-hydroxyhexane;1,6-(N,N-butylmethylaminooctyl)butane;1,6-(N,N-butylmethylaminooctyl)octane; 1,6-(N,N-butylmethyl aminoxyl)-2-hydroxypropane; 1,6-[2-(N-methylaminooctyl)ethanol]hexane;1,6-[2-(N-methyl aminooctyl)Ethanol(EO)₅]hexane; 1,6-[2-(N-methylaminooctyl)ethanol(PO)₅]hexane; 1,6-[2-(N-methyl aminooctyl)ethanol(EO)₅(PO)₅]hexane; 1,6-[2-(N-methyl aminooctyl)ethanol(EO)₅]hexane;1,6-[2-(N-methyl aminooctyl)ethanol]dipropylether; 1,6-[2-(N-methylaminooctyl)ethanol]-2-hydroxypropane;1,6-[2-(N-methylaminooctyl)Ethanol]butane; 1,6-[2-(N-methylaminooctyl)ethanol]octane; and a mixture thereof.

In addition, in the surfactant system of the present invention, when A₁and A₂ in a compound of Chemical Formula 4 are independently orsimultaneously C1-20 saturated or unsaturated chain groups, benzylgroups, hydroxy ethyl groups, or hydroxy ethyl groups to which 1-20ethylene oxide or propylene oxide groups are attached, the compoundcomprises a cationic group.

Among the compounds of Chemical Formula 4, preparation thereofcomprising a cationic group is similar to with the above Equations 3 to5, and the following two methods can be used.

First, the cationic compound of Chemical Formula 4 can be prepared by a)reacting a secondary amine with a compound comprising a C1-20 saturatedor unsaturated chain group, a benzyl group, a hydroxy ethyl group, or ahydroxy ethyl group to which 1 to 20 ethylene oxide or propylene oxidegroups are attached, under alkaline conditions to prepare a tertiaryamine; and b) adding a compound of the following Chemical Formula 5 tothe obtained tertiary amine to cause quaternarization.[Chemical Formula 5]

-   -   wherein n is an integer of 1 to 20; X′ is a halogen atom; R₅ is        hydrogen, or a C1-20 alkyl or alkyl group comprising at least        one double bond, hydroxyl group, or ether group.

Alternatively, the cationic compound of Chemical Formula 4 can beprepared by a) reacting a secondary amine with a compound of ChemicalFormula 5 under alkaline conditions to prepare a tertiary amine; and b)binding a compound comprising a C1-20 saturated or unsaturated chaingroup, a benzyl group, a hydroxy ethyl group, or a hydroxy ethyl groupto which 1 to 20 ethylene oxide or propylene oxide groups are attachedto the obtained tertiary amine, to cause quaternarization.

First, a secondary amine corresponding to the object of the presentinvention and a compound comprising a C1-20 saturated or unsaturatedchain group, a benzyl group, a hydroxy ethyl group, or a hydroxy ethylgroup to which 1 to 20 ethylene oxide or propylene oxide groups areattached are reacted while heating under basic conditions to prepared atertiary amine, and then it is reacted with a linker of the aboveChemical Formula 4 to cause quaternarization, one example of which is asshown in the following Equation 6.

-   -   wherein R is a C1-20 saturated or unsaturated chain group, a        benzyl group, a hydroxy ethyl group, or a hydroxy ethyl group to        which 1 to 20 ethylene oxide or propylene oxide groups are        attached; n is an integer of 1 to 20; X is a halogen atom, a        sulfate group, or an acetate group; X′ is a halogen atom; and R₅        is hydrogen, or a C1-20 alkyl or allyl group comprising at least        one double bond, hydroxyl group, or ether group.

Alternatively, a secondary amine corresponding to the object of thepresent invention is reacted with a compound of the above ChemicalFormula 5 to synthesize a tertiary amine under alkaline conditions, andthen it is reacted with a compound comprising a C1-20 saturated orunsaturated chain group, a benzyl group, a hydroxy ethyl group, or ahydroxy ethyl group to which 1 to 20 ethylene oxide or propylene oxidegroups are attached, to quaternarize, one example of which is as shownin the following Equation 7.

-   -   wherein R is a C1-20 saturated or unsaturated chain group, a        benzyl group, a hydroxy ethyl group, or a hydroxy ethyl group to        which 1 to 20 ethylene oxide or propylene oxide groups are        attached; n is an integer of 1 to 20; X is a halogen atom, a        sulfate group, or an acetate group; X′ is a halogen atom; and R₅        is hydrogen, or a C1-20 alkyl or allyl group comprising at least        one double bond, a hydroxyl group, or an ether group.

Among the cationic compounds of Chemical Formula 4, bis-forms can beprepared through the pathway of the above Equations 6 or 7.

In addition, the cationic compound comprising 3 or more cationic groupsin one molecule can be obtained by reacting an equal number of moles ofa secondary amine and epichlorohydrin in an alcohol solvent tosynthesize an intermediate, and then polymerizing the intermediate. Thepolymerization degree of the cationic compound can be controlled bycontrolling time and temperature of polymerization. The synthesispathway of the cationic compound of such an oligomer or polymer form isas shown in the following Equation 8.

-   -   wherein R₁ and R₂ are as defined in the above, and n is an        integer of 1 to 20.

In the present invention, a cationic compound can be easily synthesizedby selecting an appropriate method according to a desired compound. Thesynthesized compound can be confirmed by NMR and MASS analyses.

The compound of Chemical Formula 3 comprising a cationic group ispreferably selected from a group consisting of dimethyloctylethoxyammonium, dimethyl decyl ethoxy ammonium, dimethyl lauryl ethoxyammonium, dimethyloctylethanol (EO)₅ ammonium, dimethyldecylethanol(EO)₅ ammonium, dimethyllaurylethanol (EO)₅ ammonium,dimethyloctylethanol (EO)₁₀ ammonium, dimethyldecylethanol (EO)₁₀ammonium, dimethyllaurylethanol (EO)₁₀ ammonium, dimethyloctylethanol(EO)₁₅ ammonium, dimethyldecylethanol (EO)₁₅ ammonium,dimethyllaurylethanol(EO)₁₅ ammonium, trimethyloctyl ammonium,tridecyllauryl ammonium, trimethyllauryl ammonium,1,6-[2-(N-dimethylamino)ethanol]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol]hexane, 1,6-[2-(N,N-butylmethylamino)ethanol]hexane, 1,6-[2-(N,N-methyloctylamino)ethanol]hexane,1,6-[2-(N,N-dodecylmethyl amino)ethanol]hexane,1,8-[2-(N-dimethylamino)ethanol]octane,1,8-[2-(N,N-ethylmethylamino)ethanol]octane, 1,8-[2-(N,N-butylmethylamino)ethanoljoctane, 1,8-[2-(N,N-methyloctylamino)ethanol]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol]octane,1,6-[2-(N,N-dimethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane,1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₄]octane,1,8-[p2-(N,N-butylmethylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₄]octane,1,8-(2-(N,N-dodecylmethylamino)ethanol(EO)₄]octane,1,6-[2-(N-dimethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N-dimethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N-dimethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]octane, and a mixturethereof.

In addition, the surfactant system of the present invention uses acompound that can be mixed with the compound of Chemical Formula 1, 2,or 4 to obtain a mixed system with superior phase stability as theanionic surfactant. For this, generally used anionic surfactantcompounds can be applied, and particularly, a carboxylic acid saltcompound such as soap, a higher alcohol, or an alkyl ether sulfated, anolefin-sulfonated alkali salts, a sulfonates comprisingalkylbenzensulfonate, and a phosphates produced by phosphorylation of ahigher alcohol can be used. Examples include sodium lauryl sulfonateSLS), sodium lauryl ether sulfonate (SLES), a linear alkyl benzenesulfonate (LAS), a monoalkyl phosphate (MAP), acyl isethionate (SCI),alkyl glyceryl ether sulfonate (AGES), acyl glutamate, acyl taurate, afatty acid metal salt, etc., and preferably SLS, SLES, LAS, or SCI isused.

Also, the surfactant system of the present invention preferably uses acompound that is mixed with an anionic surfactant and the compound ofChemical Formula 1, 2, or 4 to show superior phase stability as anon-ionic surfactant. In the surfactant system of the present invention,the non-ionic surfactant is preferably selected from a group consistingof an alcohol ethoxylate, an alkyl phenol ethoxylate,alkylpolyglycosides, an amine oxide, an alkanolamide, and a mixturethereof.

Also, the surfactant system of the present invention preferably uses acompound that is mixed with an anionic surfactant and the compound ofChemical Formula 1, 2, or 4 to show superior phase stability as acationic surfactant. As the cationic surfactant used in the presentinvention, a commonly used cationic surfactant can be used. For example,it is selected from a group consisting of an amine salt form compound, acompound comprising quaternary ammonium, a monoalkyl dimethyl aminederivative, a dialkyl monomethylamine derivative, an imidazolinederivative, a quaternary ammonium compound of a Geminic form, anoligomeric form, and a mixture thereof.

In the mixed system prepared under the above conditions, changes inphysical properties of an anionic surfactant (for example, SLS) can beconfirmed by measuring the changes of the Krafft point, foam properties(initial foam and foam-maintaining property), surface tension, andstability to hard water.

The surfactant system of the present invention improves the Krafft pointwhen a surfactant is separated under a cooling condition to 0° C. orless, by mixing the compound of Chemical Formula 1, 2, or 4 with ananionic surfactant, which indicates that phase stability of thesurfactant system is very superior at a low temperature.

Particularly, a compound of Chemical Formula 4 comprising a non-ionicgroup shows superior phase stability even if the mixing ratio is low.Therefore, a disadvantage of anionic surfactants, separation at lowtemperature, can be compensated by mixing the non-ionic compound ofChemical Formula 4 with an anionic surfactant, which can be helpful formaintaining phase stability of a product comprising the surfactant inthe wintertime.

Also, as a result of testing foamability (initial foamability and foamstability), initial foamability of the mixed system is shown to be equalto an anionic surfactant, and foam stabilized for a long time regardlessof mixing ratio, and although initial foam production is superior, foamgradually decreases as time passes. This means that foaming property ofproducts can be controlled by selecting and applying a non-ioniccompound to prescription according to products including dish washingdetergent, shampoo, body cleanser, laundry detergent, etc.

As for a change in surface tension, it decreases as the mixing ratio ofthe non-ionic compound increases, and a constant surface tension isobtained even at a very low concentration, from which it can bepredicted that a mixed system has a lower cmc than an anionic surfactant(SLS). Such low surface tension and cmc mean that even a small amountcan show superior cleaning power.

Stability to hard water for the mixed system increases by about twicecompared to using an anionic surfactant alone. Thus it can be applied toa product that requires cleaning with water comprising a lot of positivemetal ions such as dish washing detergent or laundry detergent. Also,the increase in stability to hard water indicates that an anionicsurfactant and non-ionic compound form a mixed micelle. As the anionicsurfactant and non-ionic compound better form a mixed micelle, physicalproperties of a mixed surfactant can be sufficiently changed.

In addition, a non-ionic compound prepared using a secondary amine towhich an average of 2 to 15 moles of ethylene oxide (EO) or propyleneoxide (PO) are added can form a mixed system with a non-ionic surfactantor a mixture of an anionic surfactant and a cationic surfactant tochange physical properties.

Also, the surfactant system of the present invention improves the Krafftpoint when a surfactant is separated under a cooling condition to 0° C.or less, by mixing a cationic compound of Chemical Formula 3 with ananionic surfactant, which indicates that phase stability of thesurfactant system is superior at low temperatures.

For the Krafft point, the mixed system of the present invention shows 0°C. or less under most sample conditions, which indicates that it ishardly influenced by the length of an alkyl group of a cationic compoundand the mixing ratio. Therefore, a disadvantage of an anionicsurfactant, separation at low temperatures, can be compensated by mixingthe cationic additive with an anionic surfactant, which can be a largehelp in maintenance of phase stability of products in the wintertime.

In addition, in the case of a mixed system comprising a cationiccompound, results of testing foamability (initial foamability and foamstability) show that as an alkyl group of the cationic compounds becomeslonger, when the mixing ratio is 2/0.75 or more, initial formability ofa mixed system decreases and foam-stability becomes lower. This is aproperty required for dishwashing detergent or laundry detergent for adrum washer in which plenty of foam is initially produced like ananionic surfactant and foam is easily broken down as used. Particularly,in the case of a mixed system using a cationic compound in which adodecyl group is introduced as an alkyl group, little foam is produced.From these results, it can be seen that a cationic compounds can beapplied as an antifoaming agent for a prescription of a productcomprising an anionic surfactant as a main compound (for example, for alow foaming washing detergent, etc.).

For a change in surface tension, in the case a mixing ratio is 2/0.1 ormore, as the mixing ratio of the cationic compound increases, surfacetension decreases, and a constant surface tension is maintained even atlow concentration, from which it can be predicted that a mixed systemcan have a lower cmc than an anionic surfactant (SLS). Such low surfacetension and cmc means that even if with a small amount of cationiccompound can increase cleaning property.

The mixed system shows very improved stability to hard water in the caseof a cationic compound having an alkyl group of a butyl group or more,or in the case the mixing ratio with an anionic surfactant is 2/0.5 ormore. Particularly, in the case when a cationic compound includes abutyl group, a mixed system shows a stability to hard water increase ofapproximately 4 times compared to using an anionic surfactant alone.Thus, it can be applied for products for cleaning using water comprisingmany positive metal ions such as for dish washing detergent or laundrydetergent. Also, an increase in stability to hard water indicates thationicity of the anionic surfactant binds with cationic compounds to forma complex. As an anionic surfactant and a cationic compound bindstrongly, a smaller amount of a cationic compound can sufficientlychange physical properties of an anionic surfactant.

In order to compare capacities of the cationic compound of ChemicalFormula 4 for changing physical properties of an anionic surfactant,quaternary ammonium compounds comprising alkyl groups of the same lengthand a hydroxy ethyl group were prepared and physical properties wereevaluated under the same conditions. As results, the cationic compoundof the present invention showed a lowered Krafft point, an improvedfoam-controlling power, a lowered surface tension, and improvedstability to hard water even with a low mixing ratio compared to acontrol. From these results, it can be seen that as cationic groups inone molecule increase, a capacity for changing physical properties of ananionic surfactant is improved.

In addition, when a cationic compound of Chemical Formula 2 or 4 isprepared using a secondary amine in which an average of 2 moles ofethylene oxide (EO) and 4 moles of propylene oxide (PO) are added to ahydroxyl group, the capacity for changing physical properties of ananionic surfactant can also be improved.

As explained, the mixed surfactant system of the present invention inwhich a compound of the above Chemical Formula 1, 2, or 4 and an anionicsurfactant are mixed has very superior surface active effects, and thus,if included in solid, liquid, gel, or paste types detergents, forexamples, products such as shampoo, skin cleanser, soap, dish washingdetergent, house detergent, industrial detergent, toothpaste, powderdetergent, etc. and additive prescriptions, products with effectssuperior to the conventional products can be provided.

The present invention will be explained in more detail with reference tothe following Examples. However, these are to illustrate the presentinvention, and the present invention is not limited to them.

EXAMPLE

1-1-1. Synthesis of Mono-Type Quaternary Ammonium Cationic Compound

5 kinds of mono-type compounds comprising one quaternary ammonium groupas a representative cationic group that changes physical properties ofan anionic surfactant in a mixed system with the anionic surfactant, and2 kinds of compounds in which ethylene oxide (EO) is added to a hydroxylgroup of a mono-type compound as a non-ionic hydrophilic group weresynthesized by the following method.

Synthesis Example 1

Synthesis of N-(dimethyldodecylamino)ethanol

To a three-necked flask, isopropyl alcohol (IPA; 40 g), dodecyl chloride(153 g; 0.75 mol), and 2-(dimethylamino)ethanol (44.6 g; 0.5 mol) wereintroduced, and sodium iodide (2.4 g) was added as a catalyst and thenthe mixture was refluxed. Amount of amine was measured to confirm thereaction. 5 hours after elevating the temperature of the reactor to 120°C., the reaction proceeded over 95%. The reaction product was mixed withacetone and cooled to be crystallized. After recrystallization, theproduct obtained by filtration was immediately dried in vacuum.

Molecular weight: 293 g/mol

Yield: 67%, white solid

Solubility: very strong hygroscopicity, insoluble in acetone

Mass spectrometry (FAB+, m/e): 551, 258 [M-Cl]+, 265

¹H NMR(solvent; D₂O, ppm): 0.8620[3H], 1.2832[18H], 1.6276[2H], 3.1601[6H], 3.3645[2H], 3.4859[2H], 4.0124[2H]

Elementary analysis: C16H36ONCl

Theoretical value: C 65.38%, H 12.35%, N 4.77%

Calculation value: C 64.00%, H 12.80%, N 5.60%

Synthesis Example 2

Synthesis of N-(dimethyloctylamino)ethanol

To a three-necked flask, IPA (18.7 g), octyl chloride (66.9 g; 0.45mol), and 2-(dimethylamino)ethanol (26.74 g; 0.3 mol) were introducedand the reactor was heated to reflux the mixture. Amount of amine wasmeasured to confirm the reaction. 6 hours after elevating thetemperature of the reactor to 110° C., the reaction proceeded over 95%.The reaction product was mixed with acetone and cooled to becrystallized. The recrystallized product was filtered and thenimmediately dried in vacuum.

Molecular weight: 238 g/mol

Yield: 42%, white solid

Solubility: very strong hygroscopicity, insoluble in acetone

Mass spectrometry (FAB+, m/e): 439, 202[M-Cl], 200

Synthesis Example 3

Synthesis of N-(butyidimethylamino)ethanol

To a three-necked flask, IPA (29 g), 1-chlorobutane (70 g; 0.75 mol) and2-(dimethylamino)ethanol (44.6 g; 0.5 mol) were introduced, and NaI (1.4g) was added as a catalyst and then a reactor was heated to reflux themixture. Amount of amine was measured to confirm the reaction, and thereaction was continued for 21 hours. The reaction product was mixed withacetone and cooled to be crystallized, and the recrystallized productwas filtered and then immediately dried in vacuum.

Molecular weight: 182 g/mol

Yield: 85%, white solid

Solubility: very strong hygroscopicity, insoluble in acetone

Mass spectrometry (FAB+, m/e): 327,146[M-Cl]⁺

¹H NMR(solvent; D₂O, ppm): 0.9657[3H], 1.3837[2H], 1.7449[2H],3.1427[6H], 3.3831[2H], 3.4904[2H], 4.0445[2H]

Elementary analysis: C₈H₂₀ONCl

Theoretical value; C 52.88%, H 11.09%, N 7.71%

Calculation value; C 52.20%, H 11.70%, N 7.30%

Synthesis Example 4

Synthesis of N-(dimethylethylamino)ethanol

To a three-necked flask, IPA (40 g), iodo ethane (117 g; 0.75 mol), and2-(dimethylamino)ethanol (44.6 g; 0.5 mol) were introduced and NaI (2 g)was added as a catalyst and then a reactor was heated to reflux themixture. The reaction product was poured into n-hexane and then cooledto be crystallized, and the crystallized product was filtered andimmediately dried in vacuum.

Molecular weight: 245 g/mol

Yield: 110 g (90%) yellow solid

Solubility: very strong hygroscopicity, soluble in acetone, insoluble inn-hexane.

Mass spectrometry: (FAB+, m/e): 363,118[M-I]⁺

¹H NMR (solvent; D₂O, ppm): 1.3763[3H], 3.1266[6H], 3.4672[2H+2H],4.0457[2H]

Elementary analysis: C₆H₁₆ONI

Theoretical value; C 29.4%, H 6.6%, N 5.7%

Calculation value; C 28.8%, H 6.9%, N 5.2%

Synthesis Example 5

Synthesis of N-(trimethylamino)ethanol

To a three-necked flask, IPA (37 g), iodo methane (142 g; 1.0 mol), and2-(dimethylamino)ethanol (44.6 g; 0.5 mol) were introduced and mixed tocomplete a reaction. At this time, simultaneously with adding thereactants, an exothermic reaction occurred to complete the reaction. Thereaction product was poured into acetone and then cooled to becrystallized, and the crystallized product was filtered and thenimmediately dried in vacuum.

Molecular weight: 231 g/mol

Yield: 76%; white solid

solubility: very strong hygroscopicity, insoluble in acetone

Mass spectrometry (FAB+, m/e): 335, 154, 104[M-I]⁺

¹H NMR (solvent; D₂O, ppm): 3.1876[9H], 3.5024[2H], 4.0540[2H]

Elementary analysis: C₅H₁₄ONI

Theoretical value; C 25.99%, H 6.11%, N 6.11%

Calculation value; C 26.19%, H 6.27%, N 5.64%

1-1-2. Synthesis of Compound wherein Non-Ionic Group (EO) is Bound toMono-Type Cationic Compound

Synthesis Example 6

Synthesis of N-dimethyldodecylamino)ethanol (EO)2

To a three-necked flask, IPA 47.6 g, dodecyl chloride (91.8 g; 0.45mol), and 2-(dimethylamino)ethanol (EO)₂ (79 g; 0.3 mol) were introducedand NaI (1.7 g) was added as a catalyst. 7 hours after elevating thetemperature to 110° C., the reaction proceeded over 95%. The product wasseparated and purified using column chromatography with silica gel.

Molecular weight: 382 g/mol

Yield: 26%; transparent oil

Solubility: very strong hygroscopicity, soluble in acetone

Mass spectrometry (FAB+, m/e): 478[EO=5], 434[EO=4], 390[EO=3],346[EO=2], 302[EO=1], 258[EO=0]

Synthesis Example 7

Synthesis of N-(dimethyldodecylamino ethanol (EO)₄

To a three-necked flask, IPA (47.6 g), dodecyl chloride (92 g; 0.45mol), and 2-(dimethylamino)ethanol (EO)₄ (143.7 g; 0.3 mol) wereintroduced and NaI (2.4 g) was added as a catalyst, and then afterelevating the temperature to 110° C., the reaction was proceeded for 12hours. The reaction product was separated and purified using columnchromatography with silica gel.

Molecular weight: 507 glmol

Yield: 21%; light brown oil

Solubility: very strong hygroscopicity, soluble in acetone

Mass spectrometry (FAB+, m/e): 610[EO=8], 566[EO=7], 522[EO=6],478[EO=5], 434[EO=4], 390[EO=3], 346[EO=2], 302[EO=1]

1-2. Studies for Changes in Physical Properties of SLS of a Mixed Systemwhen Mixing SLS with Cationic Compounds of Mono-Type Quaternary AmmoniumForms (Synthesis Examples 1 to 5) and Cationic Compounds in which aNon-Ionic Group is Added to a Mono-Type (Synthesis Examples 6, 7)

Examples 1 to 7

Sodium lauryl sulfate (SLS; Sigma reagent; molecular weight 288 g/mol),a cationic compound prepared in the above Synthesis Examples 6 to 12,and alkanolamide were mixed in a mole ratio of 1:1:0.001. Concentrationof a mixed system was controlled to 2% aqueous solution, and a mixingratio of SLS and the cationic compound was controlled to 1:1 by moleratio so that changes in physical properties could be remarkably shown(Table 1). TABLE 1 Sample conditions when measuring Krafft point andfoaming property Added amount per 100 ml of water (g), (mole ratio ofSLS: cationic compound = 1:1) SLS compound 1 compound 2 compound 3compound 4 compound 5 compound 6 compound 7 Example 1 0.98 1.02 — — — —— — Example 2 1.10 — 0.90 — — — — — Example 3 1.22 — — 0.78 — — — —Example 4 1.07 — — — 0.93 — — — Example 5 1.10 — — — — 0.90 — — Example6 0.86 — — — — — 1.14 — Example 7 0.76 — — — — — — 1.24

[Experiment 1]

In order to measure changes in physical properties in the mixed systemsof Examples 1 to 7, changes in Krafft point, initial foamability, foamstability, stability to hard water, cmc, and surface tension weremeasured.

1) Measurement of Krafft Point

In the Krafft point test, the temperature when the solution cloudedthrough the previous test becomes transparent again while elevating thetemperature were measured. The results show that, as cloudiness beginsat a lower temperature and the solution becomes transparent at a lowertemperature, the solution maintains a more stable condition. Samples ofExamples 1, 2, 6, and 7 showing cloudiness when mixing were not tested,but samples of Examples 3 to 5 were tested. Test results are as shown inthe following Table 2. TABLE 2 Results of measuring change in Krafftpoint in a mixed system When lowering When elevating temperature(° C.)temperature(° C.) Example 3 <0 — Example 4 <0 — Example 5 <0 —

As shown in Table 2, Examples 3 to 5 improved the Krafft point to under0° C. when compared to SLS alone. This indicates that in most liquiddetergents of aqueous solution phases, the surfactant is not separatedfrom the solution even at a low temperature and it can maintain a stablephase.

2) Measurement of Initial Foamability and Foam Stabilty in a MixedSystem

As samples for measuring initial foamability and foam stability, samplesprepared under the same conditions as those used for measuring Krafftpoint were used (Table 14). However, samples of Examples 1, 2, 6, and 7showing cloudiness when mixing were not tested, and samples of Examples3 to 5 were tested. The semi-micro TK method was used for measurement,and mean values were taken after measuring three times. Results ofmeasuring foaming property are as shown in Table 3. TABLE 3 Results ofinitial foamability and foam stability (unit: ml) 0 min. 1 min. 2 min. 3min. 4 min. 5 min. Example 3 115 38 10 10 10 10 Example 4 140 65 35 1010 10 Example 5 155 95 60 50 40 40

As shown in Table 3, Examples 3 to 5 showed almost the same level ofinitial foamability with SLS alone. However, in the test measuring foamstability, the mixed systems of Examples 3 to 5 showed results that foamdisappeared only after 2 minutes. Also, as the alkyl group of thecationic compound becomes longer, foam stability became lower.

As can be seen from these results, the mixed systems of Examples 3 to 5of the present invention maintain initial foamability of the anionicsurfactant while produced foam can be removed within a short time, andthe cationic compound has very superior effects for inhibiting foammaintenance.

3) Evaluation of Stability to Hard Water

After dissolving 11.69 g of CaCl2.2H₂O in 1 liter of water to preparehard water of 10,000 ppm, it was slowly added to a 0.5% aqueous solutionsample, and stability to hard water was evaluated using the amount ofhard water added until cloudiness began. The results are shown in Table4. Samples of Examples 1, 2, 6, and 7 showing cloudiness when mixingwere not tested. TABLE 4 Results of stability to hard water Hard waterSample (0.5% aqueous Added amount of 10,000 ppm concentration solution)hard water (ml) (ppm) Example 3 6.6 619 Example 4 2.8 272 Example 5 3.0291

As shown in Table 4, Example 3 showed improved of about twice that ofSLS alone, and Examples 4 and 5 showed levels of stability to hard watervery similar to that of SLS.

4) Measurement of Changes in Surface Tension and cmc in a Mixed System

Changes in surface tension and cmc in the mixed systems of Examples 1 to7 were measured using a processor tensiometer K12 from the KrussCompany. Samples of which surface tensions were to be measured wereprepared by mixing SLS and a cationic compound in a mole ratio of 1:1,wherein deionized water was used as water, and a container formeasurement was immersed in a cleaning solution for more than 3 hours,washed with water and acetone, dried in an oven, and then used. Resultsof measuring surface tension and cmc are shown in Table 5. TABLE 5Results of measuring changes in surface tension and cmc (25° C.) Surfacetension cmc (10⁻³ M) (mN/m) Example 1 0.06 25 Example 2 0.84 29 Example3 3.3 35 Example 4 3.8 38 Example 5 5.8 39 Example 6 0.11 26 Example 70.2 36

As can be seen from Table 5, the mixed systems of Examples 1 to 7 mixingSLS and cationic compounds showed decreased surface tensions by 13-44%compared to SLS. Particularly, the mixed systems of Examples 1, 2, 6,and 7 showed results that cmc became thinner by 10 to 100 times. Thismeans that even a small amount can show superior surface active effects.

2-1. Bis-Type Cationic Compound Comprising Two Cationic Groups inMolecule

2-1-1. Synthesis of Cationic Compound

An appropriate synthesis pathway was selected according to linker lengthand alkyl group length as in Equations 1 to 3 or Equations 6 to 7, toprepare desired cationic compounds.

Synthesis Example 8

Synthesis of 1,6-[2-(N-methylamino)ethanol]hexane

To 40 g of IPA, 45 g of 2-(methylamino) ethanol (0.6 mol), 46.5 g of1,6-dichlorohexane (0.3 mol), and 48 g of Na₂CO₃ were mixed, and themixture was refluxed for 25 hours. The product was filtered, distilledunder reduced pressure, and vaccum-dried to purify it.

Molecular weight: 232 g/mol

Phase: oil phase

¹H NMR(CDCl₃, δ ppm): 1.07(4H), 1.28(4H), 2.20(6H), 2.37(4H), 2.47(4H),3.41 (4H)

Mass (FAB+): m/e 233[M+H]⁺

Synthesis Example 9

Synthesis of 1,6-[2-(N,N-dimethylamino)ethanol]hexane (using Equation 1)

To 20 g of IPA, 23.2 g of 1,6-[2-(N-methylamino)ethanol]hexane (0.1mol), 42.6 g of iodomethane (0.3 mol), and 5 g of NaI were mixed, andthen reaction was proceeded at room temperature for 2 hours. Then, theproduct was filtered, distilled under reduced pressure, dried in vacuum,and crystallized with acetone to purify it.

Molecular weight: 262 g/mol

Phase: yellow powder (hygroscopicity)

¹H NMR(D₂O, δ ppm): 1.20(4H), 1.83(4H), 3.16(12H), 3.38˜3.55(8H),4.06(4H)

Mass (FAB+): m/e 389[M2⁺⁺I]^(+,) 297, 261, 247, 217

Synthesis Example 10

Synthesis of 1,6-[2-(N,N-ethylmethylamino)ethanol]hexane (using Equation1)

To 20 g of IPA, 15.11 g of 1,6-[2-(N-methylamino)ethanol]hexane (0.065mol), 30.5 g of iodoethane (0.195 mol), and 3 g of NaI were mixed andthe mixture was refluxed for 9 hours. Then, the product was filtered,distilled under reduced pressure, dried in vacuum, and crystallized withacetone to purify it.

Molecular weight: 290 g/mol

Phase: yellow powder (hygroscopicity)

¹H MR(D₂O, δ ppm): 1.35(4H), 1.45(4H), 2.97(6H), 3.37(10H), 3.47(8H),4.04(4H)

Mass (FAB+): m/e 417[M2⁺⁺I]⁺

Synthesis Example 11

Synthesis of 1,6-[2-(N,N-butylmethylamino)ethanol]hexane (using Equation2)

To 11 g of IPA, 20.5 g of 2-(N,N-butylmethylamino)ethanol (0.156 mol),12.1 g of 1,6-dichlorohexane (0.078 mol), 33 g of Na2 CO3, and 5 g ofNaI were mixed and the mixture was refluxed for 14 hours. Then, theproduct was filtered, distilled under reduced pressure, dried in vacuum,and crystallized with acetone to purify it.

Molecular weight: 346 g/mol

Phase: oil phase

¹H NMR(D₂O, δ ppm): 1.00(6H), 1.41(8H), 1.75(8H), 3.10(6H),3.34˜3.51(12H), 4.04(4H)

Mass (FAB+): m/e 381 [M₂ ⁺⁺Cl^(−]) ⁺

Synthesis Example 12

Synthesis of 1.6-12-(N,N-methyloctylamino)ethanollhexane (using Equation2)

To 6 g of IPA, 18.76 g of 2-(N,N-methyloctylamino)ethanol (0.1 mol), 7.8g of 1,6-dichlorohexane (005 mol), 2.2 g of Na2CO3, and 2.5 g of NaIwere mixed and then the mixture was refluxed for 22 hours. The productwas filtered, distilled under reduced pressure, and dried in vacuum topurify it.

Molecular weight: 458 g/mol

Phase: oil phase

¹H NMR(D₂O, δ ppm): 0.89(6H), 1.31(24H), 1.77(8H), 3.10(6H), 3.36(8H),4.49(4H), 4.04(4H)

Mass (FAB+): m/e 493[M2⁺⁺Cl]⁺

Synthesis Example 13

Synthesis of 1,6-[2-(N N-dodecylmethylamino)ethanol]hexane (usingEguation 2)

To 10 g of IPA, 18.69 g of 2-(N,N-dodecylmethylamino)ethanol (0.077mol), 6 g of 1,6-dichlorohexane (0.39 mol) and 3 g of NaI were mixed,and the mixture was refluxed for 20 hours. The product was filtered,distilled under reduced pressure, and dried in vacuum to purify it.

Molecular weight: 570 g/mol

Phase: oil phase

¹H NMR(D₂O, δ ppm): 0.94(6H), 1.20(40H), 1.82(8H), 3.20(6H), 3.59(8H),3.69(4H), 4.09(4H)

Mass (FAB+): m/e 605[M2⁺⁺Cl⁻]⁺

[Experiment 2]

2-2. Measurement of Changes in Effects of Anionic Surfactant in a MixedSystem of Anionic Surfactant and Cationic Compound

As an anionic surfactant for measuring physical properties, sodiumlauryl sulfate (SLS; Aldrich Company reagent; purity 99% or more) wasused.

Additionally, as a cationic compound, compounds having an n value of 6among the cationic compounds of the following Chemical Formula 2a wereused (Table 6).

(wherein R is a C1-C12 alkyl group and n is 6.) TABLE 6 Kinds andmolecular weight of cationic compounds (n = 6) Synthesis SynthesisSynthesis Synthesis Synthesis Example 14 Example 15 Example 16 Example17 Example 18 Compound(R/X) C₁/I C₂/I C₄/Cl C₈/Cl C₁₂/Cl Molecular 516644 374 486 598 weight(g/mol)

Glass used in the following experiment was immersed in a cleaningsolution (KOH+IPA+water) for more than 4 hours, and washed withdistilled water and acetone, dried, and then used. Deionized water wasused for measurement.

Changes in physical properties of the anionic surfactant were measuredfor changes in Krafft point, initial foamability, foam stability,stability to hard water, surface tension, etc.

2-2-1. Measurement of Physical Properties of Cationic Compound

1) sample Conditions

1 g each of the cationic compounds of Synthesis Examples 14 to 18 weredissolved in 99 g of water to make samples of 1 wt % concentration to beused for measurement. The samples having C1, C2, and C4 alkyl groupswere transparent, but the samples having C8 and C12 alkyl groups showedcloudiness. When the carbon number of the alkyl group was C8, thesolution became transparent at 0.1 wt %, and when it was C12, thesolution became transparent at 0.01 wt %.

2) Measurement of Krafft Point of Cationic Compound

The temperature when cloudiness begins was measured while cooling thetransparent cationic compound solution (condition of loweringtemperature). Additionally, the temperature when the solution becomestransparent was measured while elevating the temperature of the cloudysolution (condition of elevating temperature).

SLS showed results that cloudiness occurred at 2˜3° C. when lowering thetemperature, and the solution became transparent again at 14° C. whenelevating the temperature. Meanwhile, cationic compounds of the presentinvention did not show cloudiness even at 0° C. when lowering thetemperature. In cases where cloudiness did not occur at 0° C., tests ofelevating temperature were not conducted.

3) Measurement of Foaming Property (Initial Foamability and FoamStability)

Foamability-related tests were conducted using a semi-micro TK method,and the results are shown in Table 7. The tests were repeated threetimes and a mean value was taken. A 1% solution was used in the tests,and in the case of Synthesis Example 18, a cloudy solution was used formeasurement. TABLE 7 Results of measuring foaming property of cationiccompounds (unit ml) (ml) 0 min. 1 min. 2 min. 3 min. 4 min. 5 min.Synthesis Example 14 C₁ No foaming Synthesis Example 15 C₂ No foamingSynthesis Example 16 C₄ No foaming Synthesis Example 17 C₈ No foamingSynthesis Example 18 C₁₂ 213 203 190 128 120 105

As shown in Table 7, Synthesis Examples 14 and 16, cationic compoundshaving short alkyl chains, did not produced foam, but Synthesis Example18 produced a comparatively weak foam with initial foamability of 213 mland foam stability after 5 minutes of 105 ml.

4) Measurement of Surface Tension

Surface tensions of cationic compounds of Synthesis Examples 14 to 18were measured using a tensiometer K12 of the Kruss Company. A ringmethod was used, and after measuring 5 times, a mean value was taken.Solutions of 1%, 0.1%, 0.01%, and 0.001% by weight ratio of each of thecationic compounds were prepared to use for the tests. Results ofsurface tension are shown in Table 8. TABLE 8 Results of measuringsurface tension of cationic compound (unit: mN/m) concentration 1% 0.1%0.01% 0.001% Synthesis C₁ 59.49 70.04 71.41 — Example 14 Synthesis C₂61.35 68.63 71.53 — Example 15 Synthesis C₄ 37.45 51.95 61.98 — Example16 Synthesis C₈ 27.91 33.90 47.50 — Example 17 Synthesis C₁₂ 30.30 30.7030.85 47.44 Example 18

As shown in Table 8, Synthesis Example 18 showed a comparatively lowsurface tension in the measurement sample concentration range, but othercationic compounds showed high surface tension values.

5) Measurement of Stability to Hard Water

Hard water of 10,000 ppm prepared by dissolving 11.69 g of CaCl2.2H₂O in1 L of water was used for the tests. Stability to hard water wasmeasured by adding hard water until pearl is appear, using 0.5% (weightratio) of the cationic compound and 100 ml of the sample. This test wasrepeated by three times, and a mean value was taken. Since the cationiccompound does not carry a negative charge, precipitation was notproduced in hard water. However, C12 showed cloudiness at 0.5%, and itwas not measured.

2-2-2. Measurement of Changes in Physical Properties of SLS of MixedSystem of Anionic Surfactant (SLS) and Cationic Compound of SynthesisExample 14 (R═CI/n=6)

Examples 8 to 13

Sample solutions were prepared with mole ratios of the anionicsurfactant (SLS) and the cationic compound of Synthesis Example 14 asshown in Table 9, and all the prepared sample solutions weretransparent. A non-ionic surfactant alkanolamide was added so that itsmole ratio for SLS became 1:0.001. TABLE 9 Mixed system measuring sampleExample 8 Example 9 Example Example Example Example 13 Mixed 2/1.02/0.75 2/0.5 2/0.25 2/0.1 2/0.01 amount/rat SLS/C1(g) 0.53/0.470.60/0.40 0.69/0.31 0.82/0.18 0.92/0.08 0.991/0.009 Phase transparenttransparent transparent transparent transparent transparent stability

[Experiment 3]

1) Measurement of Krafft Point

Krafft points of Examples 8 to 13 (mixed systems of SLS and cationiccompound) were measured, and the results are shown in Table 10. TABLE 10Measurement of Krafft point of mixed systems (unit ° C.) Example 8Example 9 Example

Example

Example

Example

When lowering <0 <0 <0 <0 <0 −0.5 temperatur

When elevating — — — — — 13 temperatur

As shown in Table 10, Krafft points of all the samples were lowered to0° C. or less. However, in the case of Example 13 with a mixing ratio of2/0.01, the solution became opaque at −0.5° C., and when elevating thetemperature, it became transparent again at 13° C., which indicates thatsolubility (stability) at low temperature was improved compared to SLS.In the case of other samples maintaining transparency even at 0° C. orless, measurement of Krafft point while elevating temperature could notbe conducted.

2) Measurement of Foaming Property (Initial Foamability and FoamStability)

Results of measuring foaming property are shown in Table 11. TABLE 11Results of measuring foaming property of mixed system (unit ml) 0 min. 1min. 2 min. 3 min. 4 min. 5 min. Example 8 175 118 80 65 58 53 Example 9193 160 128 100 85 78 Example 10 223 205 185 180 175 175 Example 11 218210 210 205 203 195 Example 12 225 223 220 220 220 218 Example 13 238233 230 230 230 223

As shown in Table 11, as the mixing ratio of the cationic compoundbecomes lower, the initial foamability and foam stability tended tobecome more similar to those of SLS. In Examples 8, 9, and 10, initialfoamability decreased and foam was broken easily. For other mixingratios, as the mixing ratio of the cationic compounds increased, initialfoamability and foam stability slightly decreased, but a significantdifference was not shown.

3) Measurement of Surface Tension

Results of measuring surface tension are shown in Table 12. TABLE 12Results of measuring surface tension change of mixed system (roomtemperature) Concentration 1% 0.1% 0.01% Example 8 35.04 36.24 36.45Example 9 33.12 36.27 36.32 Example 10 36.8 37.08 36.6 Example 11 35.4337.29 36.11 Example 12 35.47 31.76 45.66 Example 13 35.7 25.86 48.12

As shown in Table 12, Example 13 showed almost the same surface tensionvalue as SLS, but as the mixing ratio of the cationic compoundincreased, the surface tension ended to decrease. The results that thesurface tension decreased and there was no change at a low concentrationmean that cmc is low, which indicates that only a small amount of thecompound can show superior effects to cleaning.

4) Measurement of Stability to Hard Water for Mixed System

Results of measuring stability to hard water for a mixed system areshown in Table 13. TABLE 13 Measurement of change in stability to hardwater for mixed system Example 8 Example 9 Example 10 Example 11 Example12 Example 13 2/1.0 2/0.75 2/0.5 2/0.25 2/0.1 2/0.01 1^(st) 8.6 5.1 3.22.3 2.0 2.4 2^(nd) 8.4 5.2 3.4 2.3 1.9 2.4 Mean(ml) 8.5 5.15 3.3 2.31.95 2.4 Hard water 780 490 320 220 190 230 concentration (ppm)

As shown in Table 13, as the mixing ratio of the cationic compoundincreases, the added amount of hard water increased. However, thedifference between stabilities to hard water of Examples 8 and 13 wasapproximately 2 times.

2-2-3. Measurement of Changes in Physical Properties of SLS in a MixedSystem of SLS and Cationic Compound of SYNTHESIS Example 15 (R═C2/n=61

Examples 14 to 19

An anionic surfactant and the cationic compound of Synthesis Example 15(R═C2/n=6) were mixed in a mole ratio as shown in Table 14 to preparemixed system samples to be used for measurement, and all the preparedsample solutions were transparent. At this time, a non-ionic surfactantethoxylated fatty alcohol was added so that mole ratio for SLS became1:1. TABLE 14 Example 14 Example 15 Example 16 Example 17 Example 18Example 19 Mole ratio 2/1.0 2/0.75 2/0.5 2/0.25 2/0.1 2/0.01 SLS/C₂(g)0.51/0.49 0.59/0.41 0.68/0.32 0.81/0.19 0.91/0.09 0.99/0.01 Phasetransparent transparent transparent transparent transparent transparentstability[Experiment 4]Measurement of Physical Properties of Examples 14 to 19

1) Measurement of Change in Krafft Point of Mixed System

As results of measuring change in Krafft point of a mixed system, it asfound that the Krafft point of a mixed system tended to decrease (Table15). Samples with a mixing ratio of 2/0.25 or more showed results at 0°C. or less under a temperature drop condition, and those with a mixingratio of 2/0.25 or less showed that the Krafft point decreased comparedto SLS. TABLE 15 Example 14 Example 15 Example 16 Example 17 Example 18Example 19 Mole ratio 2/1.0 2/0.75 2/0.5 2/0.25 2/0.1 2/0.01 SLS/C₂(g)<0 <0 <0 <0 0 0.5 Phase X X X X 11˜13 12˜14 stability

2) Measurement of Changes in Initial Foamability and Foam Stability ofMixed System

The results of measuring changes in initial foamability and foamstability of a mixed system are shown in Table 16. TABLE 16 Measurementof changes in initial foamability and foam stability Mole 0 1 2 3 4 5ratio min. min. min. min. min. min. Example 2/1.0 208 165 55 45 40 40 14Example 2/0.75 195 180 45 45 45 45 15 Example 2/0.5 210 205 198 198 200200 16 Example 2/0.25 223 218 218 215 215 215 17 Example 2/0.1 235 230225 225 225 223 18 Example 2/0.01 235 233 230 228 228 225 19

As shown in Table 15, until a mixing ratio of 2/0.5, initial foamabilityand foam stability did not significantly change compared to SLS, butExamples 14 and with a mixing ratio of 2/0.75 or more showed resultsthat foam stability significantly decreased. It is considered that thesemixed systems can be applied for laundry detergent for a drum washer, orautomatic dishwashing detergent, etc. requiring the property that foamcan be broke easily during washing while maintaining initial foam.

3) Measurement of Change in Surface Tension of a Mixed System

Results of measuring surface tension of mixed system are shown in Table17. TABLE 17 Measurement of change in surface tension of mixed systemConcentration Mole ratio 1% 0.1% 0.01% Example 2/1.0 33.96 34.60 36.3614 Example 2/0.75 35.44 34.78 35.15 15 Example 2/0.5 35.84 34.85 34.4416 Example 2/0.25 35.84 34.11 36.59 17 Example 2/0.1 35.82 32.38 40.0018 Example 2/0.01 36.08 22.83 43.80 19

As shown in Table 17, Example 19 (mixing ratio of 2/0.01) showed almostthe same tendency as SLS, but as the mixing ratio of the cationiccompound increased, surface tension and cmc decreased. These resultssuggest that even with a small amount of additives, the mixed system canshow superior effects to cleaning.

4) Measurement of Change in Stability to Hard Water for Mixed System

Results of measuring change in stability to hard water are shown inTable 18. TABLE 18 Results of measuring change in stability to hardwater for mixed system Example 14 Example 15 Example 16 Example 17Example 18 Example 19 2/1.0 2/0.75 2/0.5 2/0.25 2/0.1 2/0.01 1^(st)12.15 7.05 4.40 2.90 2.35 2.90 2^(nd) 11.85 7.20 4.30 3.05 2.5 2.55 Mean12.0 7.12 4.35 2.98 2.43 2.73 Hard water 1071 665 417 289 237 266concentration

As shown in Table 18, as the mixing ratio of the cationic compoundincreased, stability to hard water increased, and compared to theresults of Examples 8 to 13 (carbon number of alkyl group is C1),stability to hard water generally increased at the same mixing ratio.Particularly, Examples 14 to 16 with a mixing ratio of 2/0.5 or moreshowed remarkable stability to hard water.

2-2-4. Measurement of Changes in Physical Properties of SLS in a MixedSystem of SLS and Cationic Compound of Synthesis Example 16 (R═C4/n=6)

Examples 20 to 25

Sample mixing conditions for measuring physical properties are shown inTable 19. As results of preparing mixed systems, all the samples showedtransparent phases in 1% aqueous solutions. The non-ionic surfactant,alkanolamide, was added so that its mole ratio for SLS became 1:0.001.TABLE 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example25 Mole ratio 2/1.0 2/0.75 2/0.5 2/0.25 2/0.1 2/0.01 SLS/C₄(g) 0.61/0.390.67/0.33 0.75/0.25 0.86/0.14 0.92/0.08 0.994/0.006

1) Measurement of Change in Krafft Point of Mixed System

Krafft points of Examples 20 to 25 were measured, and the results areshown in Table 20. TABLE 20 Results of measuring change in Krafft pointof mixed system Example 20 Example 21 Example 22 Example 23 Example 24Example 25 When dropping <0 <0 <0 <0 −1 −0.5 temperatur

When elevating — — — — 10˜12 11˜13 temperatur

As shown in Table 20, as in Example 25, even if only a small amount ofcationic compound is mixed, the Krafft point can be lowered to 0° C. orless. This means that a mixed system maintains stability in water evenat low temperature.

2) Measurement of Change in Foaming Property of Mixed System

Results of measuring foaming property are shown in Table 21. TABLE 21Results of measuring change in foaming property of mixed system 0 min. 1min. 2 min. 3 min. 4 min. 5 min. Example 180 133 63 58 55 45 20 Example178 113 73 43 38 35 21 Example 218 213 213 213 213 213 22 Example 223218 218 215 215 213 23 Example 223 223 223 220 220 218 24 Example 235230 230 230 225 225 25

As shown in Table 21, Samples of Examples 20 and 21 with a mixing ratioof the cationic compound of 2/0.75 or more showed decreased initialfoamability and a phenomenon in which foam rapidly decreased after 2minutes. Thus, it is considered that a cationic compound with a carbonnumber of 4 has superior capacity for lowering foam stabilty to cationiccompounds with short alkyl chains.

3) Measurement of Change in Surface Tension of Mixed System

Results of measuring surface tension are shown in Table 22. TABLE 22Results of measuring change in surface tension of mixed systemConcentration 1% 0.1% 0.01% Example 20 32.75 32.57 31.98 Example 2132.51 32.48 35.09 Example 22 33.56 32.89 33.37 Example 23 33.65 32.7232.87 Example 24 34.64 31.70 37.60 Example 25 35.11 26.19 48.02

As shown in Table 22, although Example 25 with a mixing ratio of thecationic compound of 2/0.01 showed almost the same surface tension valueas SLS, Examples 20 to 24 with a mixing ratio of 210.1 or more showedresults that, on the basis of a 1% solution, as the mixing ratio of thecationic compound increased, the surface tension decreased.Additionally, from the result of showing a constant surface tensionvalue to 0.01%, it can be seen that the mixed systems have a lower cmcthan SLS. This indicates that the mixed system of the present inventioncan have superior cleaning power even at a low concentration.

4) Measurement of Change in Stability to Hard Water for Mixed System

The results of measuring stability to hard water are shown in Table 23.TABLE 23 Measurement of change in stability to hard water for mixedsystem Example 20 Example 21 Example 22 Example 23 Example 24 Example 251^(st) 55 38 8.45 3.60 2.95 3.40 2^(nd) 58 38.7 8.75 3.75 2.90 3.50 Mean56.5 38.35 8.60 3.68 2.93 3.45 Hard water 3610 2772 792 355 285 352concentrati

As shown in Table 23, although Examples 23 to 25 with mixing ratios ofthe cationic compound of 2/0.25 or less did not show significantlyimproved stability to hard water compared to SLS, Examples 20 to 22 witha mixing ratio of 2/0.5 or more showed significantly improved results.On the basis of these results, it is considered that the mixed system ofthe present invention can be applied to products needed superiorcleaning power and phase stability under the heavier hard waterconditions.

2-2-5. Measurement of Change in Physical Properties of SLS in MixedSystem of SLS and Cationic Compound of Synthesis Example 17 (R═C5/n=6)

Examples 26 to 31

Conditions for preparing samples to be used for measurement are shown inTable 24. Examples 26 and 27 with respective mixing ratios of 2/0.75 and2/1.0 showed cloudiness and became clear under conditions of an aqueoussolution of a 0.001% concentration. A non-ionic surfactant, ethoxylatedfatty alcohol, was added so that its mole ratio for SLS became 1:1.TABLE 24 Example 26 Example 27 Example 28 Example 29 Example 30 Example31 Mole ratio 2/1.0 2/0.75 2/0.5 2/0.25 2/0.1 2/0.01 SLS/C₈(g) 0.54/0.460.61/0.39 0.70/0.30 0.83/0.17 0.92/0.08 0.992/0.008 Phase cloudinesscloudiness transparent transparent transparent transparent stability1) Measurement of Krafft Point of Mixed System

Results of measurement are shown in Table 25. However, because Examples26 and 27 with mixing ratios of 2/1.0 and 2/0.75 showed cloudiness at 1%aqueous solution, Krafft points were measured using 0.001% aqueoussolutions. As results, Krafft points were lowered to 0° C. or less inall samples. TABLE 25 Example 26 Example 27 Example 28 Example 29Example 30 Example 31 Mole ratio 2/1.0 2/0.75 2/0.5 2/0.25 2/0.1 2/0.01When dropping <0 <0 <0 <0 −1.5 −0.5 temperature When elevating X X X X12 12˜13 temperature2) Measurement of Change in Foaming Property of Mixed System

Results of measurement are shown in Table 26. A mixed system mixing thecationic compound with a carbon number of 8 did not show a significantdifference in initial foamability and foam stability from SLS, contraryto the previous experiments. However, the produced foam easilydisappeared with slight stirring. Thus, it can be seen that although theproduced foam is decreased easily in this mixed system, it does notdisappear under the test condition after 5 minutes. TABLE 26 Results ofmeasuring change in foaming property of mixed system Mole 0 1 2 3 4 5ratio min. min. min. min. min. min. Example 2/1.0 230 230 230 230 230230 26 Example 2/0.75 215 215 215 215 215 215 27 Example 2/0.5 200 195195 195 195 195 28 Example 2/0.25 235 235 235 235 235 235 29 Example2/0.1 233 233 233 233 233 233 30 Example 2/0.01 235 233 230 230 230 230313) Measurement of Change in Surface Tension of Mixed System

Results of measurement are shown in Table 27. Since surface tension tlargely change between a 1% aqueous solution and a 0.01% aqueous thesurface tension was measured using a 0.001% concentration of thesolution. As results, as the mixing ratio of the cabonic compound d, thesurface tension decreased at a 1% concentration, and surface slightlyincreased at a 0.001% concentration. Thus, it can be seen that of themixed system is between 0.01˜0.001%. TABLE 27 Results of measuringchange in surface tension of mixed system Mole concentration ratio 1%0.1% 0.01% 0.001% Example 2/1.0 26.94 27.49 28.15 32.04 26 Example2/0.75 26.56 27.07 28.36 33.44 27 Example 2/0.5 27.29 27.38 27.99 32.3628 Example 2/0.25 29.18 27.40 27.98 35.34 29 Example 2/0.1 30.36 27.5827.99 39.06 30 Example 2/0.01 34.91 29.19 34.43 60.95 314) Measurement of Change in Stability to Hard Water for Mixed System

Results of measurement are shown in Table 28. For samples showingcloudiness at 1% concentrations, stabilities to hard water were notmeasured. As results, at a mixing ratio of 2/0.5, stability to hardwater significantly increased. TABLE 28 Results of measuring change instability to hard water for mixed system Example 26 Example 27 Example28 Example 29 Example 30 Example 31 Mole ratio 2/1.0 2/0.75 2/0.5 2/0.252/0.1 2/0.01 1^(st) cloudiness Cloudiness 13.0 3.9 4.15 3.8 2^(nd)Cloudine

Cloudine

12.5 3.9 4.15 3.5 Mean Cloudine

Cloudine

12.75 3.9 4.15 3.65 Hard Cloudiness cloudiness 1131 375 398 352 waterconcentra

2-2-6. Measurement of Change in Physical Properties of SLS in a MixedSystem of SLS and Cationic Compound of Synthesis Example 18 (R═C12/n=6)

Examples 32 to 37

Measuring samples were prepared under conditions as shown in Table 29.Samples of Examples 32 to 34 with mixing ratios of 2/0.5 or more showedcloudiness. The sample of Example 34 became transparent at a 0.001%aqueous solution, and the others at 0.001%. The non-ionic surfactant,alkanolamide, was added so that its mole ratio for SLS became 1:0.001.TABLE 29 Example 32 Example 33 Example 34 Example 35 Example 36 Example37 SLS/ 0.47/0.53 0.55/0.45 0.64/0.36 0.78/0.22 0.90/0.10 0.989/0.011Reaction Example18 Phase cloudiness cloudiness Cloudiness transparenttransparent Transparent stability 0.001% 0.001% 0.01% transparenttransparent Transparent1) Measurement of Change in Krafft Point of Mixed System

Changes in Krafft point of the mixed systems of Examples 32 to 37 weremeasured, and the results are shown in Table 30. Examples 32 and 33 used0.001% solutions, and Example 34 used a 0.01% solution. TABLE 30 Resultsof measuring change in Krafft point of mixed system Example 32 Example33 Example 34 Example 35 Example 36 Example 37 When dropping <0 <0 <0 <0<0 −1 temperatur

When elevating — — — — — 12˜13 temperatur

As shown in Table 30, all the samples showed results that as thecationic compound was mixed, the Krafft point was lowered to 0° C. orless.

2) Measurement of Change in Foaming Property of Mixed System

Results of measuring foaming property are shown in Table 31. TABLE 31Results of measuring change in foaming property of mixed system Mole 0 12 3 4 5 ratio min. min. min. min. min. min. Example 2/1.0 20 0 0 0 0 032 Example 2/0.75 30 0 0 0 0 0 33 Example 2/0.5 193 190 190 190 190 19034 Example 2/0.25 243 240 240 240 240 240 35 Example 2/0.1 243 240 238238 238 238 36 Example 2/0.01 218 215 215 215 215 215 37

As shown in Table 31, Examples 32 and 33 produced little foam. Fromthese results, it is considered that a cationic compound with a carbonnumber of 12 can function as an antifoaming agent.

3) Measurement of Change in Surface Tension of Mixed System

Results of measuring surface tension are shown in Table 32. TABLE 32Results of measuring change in surface tension of mixed systemConcentration 1% 0.1% 0.01% 0.001% Example 32 24.35 25.79 30.80 40.31Example 33 24.74 26.86 31.90 39.93 Example 34 25.38 26.41 32.20 41.45Example 35 26.15 27.76 33.36 45.65 Example 36 27.82 29.76 35.02 50.05Example 37 36.33 31.59 48.09 —

As results, as the mixing ratio of the cationic compound increased, at a1% concentration, surface tension decreased, and as the concentrationdecreased, surface tension slightly increased. However, at a 1% aqueoussolution, as the mixing ratio of the cationic compound increased, thesurface tension decreased.

4) Measurement of Change in Stability to Hard Water for Mixed System

Results of measuring stability to hard water are shown in Table 33.TABLE 33 Results of measuring change in of mixed system Example 35Example 36 Example 37 1st 6.10 3.45 3.35 2^(nd) 6.10 3.45 3.50 Mean 6.103.45 3.43 Hard water 575 333 332 concentration

As results, since Examples 32 to 34 with a mixing ratio of the cationiccompound of 2/0.5 or more showed cloudiness at 1% aqueous solution,stability to hard water for these mixed systems could not be measured,and Examples 35 to 37 showed slightly improved stabilities to hardwater.

3-1. Synthesis of Non-Ionic Compound Comprising Aminoxide Group inMolecule.

Desired non-ionic compounds were prepared using synthesis pathways suchas in the above Equation 4 or 5.

Synthesis Example 19

Synthesis of N-Dimethyl Lauryl Amineoxide

To 42.7 g of N-dimethyl lauryl amine (0.2 mol), 27.3 g of hydrogenperoxide (0.24 mol; 30 wt % solution) was added by droplets at roomtemperature, the temperature was elevated to 40° C., and then reactionwas continued for 17 hours. After completion of the reaction, theproduct was distilled under reduced pressure and dried in vacuum topurify it.

Molecular weight: 229 g/mol

Phase: Yellow oil phase

¹H NMR(CDCl₃, δ ppm): 0.81(3H), 1.19(18H), 1.80(2H), 3.11(6H), 3.18(2H)

Mass(FAB+): m/e 230[M+H]⁺, 212

Synthesis Example 20

Synthesis of N-(2-hydroxyethyl lauryl methyl)amine

150.22 g of 2-(methylamino)ethanol (2 mol) was dissolved in 175 g ofisopropyl alcohol (IPA), and 408 g of 1-chlorodecane (2 mol) and 318 gof sodium carbonate (Na2CO3) (3 mol) were added, and then reaction wascontinued for 25 hours. After completion of the reaction, the productwas filtered, distilled under reduced pressure, and dried in vacuum topurify it.

Molecular weight: 243 g/mol

Phase: Yellow oil

¹H NMR(CDCl₃, δ ppm): 0.86(3H), 1.26(20H),2.18(3H), 2.39(2H), 2.52(2H),3.42(2H)

Mass(FAB+): m/e 244[M+H]⁺

Synthesis Example 21

Synthesis of N-(2-hydroxyethyl lauryl methyl)amineoxide

To 10.5 g of methanol, 30.64 g of N-(2-hydroxyethyl lauryl methyl)amineand 21.5 g of hydrogen peroxide (0.189 mol) were added by droplets atroom temperature, and temperature was elevated to reflux the mixture for31 hours. The product was filtered, distilled under reduced pressure,and dried in vacuum to purify it.

Molecular weight: 259 g/mol

Phase: yellow solution

¹H NMR(CDCl₃, 5 ppm): 0.81(3H), 1.23(18H), 1.69(2H), 3.14(3H), 3.29(4H),4.07(2H)

Mass (FAB+): m/e 260[M+H]⁺

Synthesis Example 22

Synthesis of 1.6-(N,N-butylmethylamino)hexane

To 92 g of IPA, 96 G OF 2-(n,n-butylmethyl)amine (1.1 mol), 77.53 g of1,6-dichlorohexane (0.5 mol) and 133 g of Na2CO3 were mixed, andreaction was continued at 70° C. for 36 hours. Then, the product wasdried, filtered, distilled under reduced pressure, and dried in vacuumto purify it.

Molecular weight: 256 g/mol

Phase: oil phase

¹H NMR(CDCl₃, δ ppm): 0.91(6H), 1.29(8H), 1.42(8H), 2.20(6H), 2.32(8H)

Mass (FAB+): m/e 257[M+H]⁺

Synthesis Example 23

Synthesis of 16-(N,N-butylmethyl amineoxyl)hexane

21.88 g of 1,6-(N,N-butylmethyl amino)hexane (0.086 mol) was dissolvedin 14 g of methanol, and 24 g of hydrogen peroxide (0.215 mol; 30 wt %solution) were slowly added. Reaction was continued for 18 hours byreflux, and then the product was distilled under reduced pressure anddried in vacuum to purify it.

Molecular weight: 288 g/mol

Phase: yellow oil phase

¹H NMR(CDCl₃, δ ppm): 0.97(6H), 1.39(8H), 1.77(8H), 3.18(6H), 3.32(8H)

Mass (FAB+): m/e 289[M+H]⁺, 170

[Experiment 5]

3-2. Evaluation of Change in Effects of Anionic Surfactant in a MixedSystem of Anionic Surfactant and Non-Ionic Compound ComprisingAmineoxide Group

As an anionic surfactant for measuring physical properties, sodiumlauryl sulfate (SLS; Aldrich Company reagent; purity 99% or more) wasused. SLS, which has a Krafft point of 2° C. (when lowering temperature)and 14° C. (when elevating temperature) and initial foamability of 233ml; maintains foam for 5 minutes almost constantly; and has a surfacetension of 35.92 mN/m at 1%, 25.19 at 0.1%, and 57.18 at 0.01%, wasused. Additionally, when measuring stability to hard water, the hardwater concentration was 310 ppm.

Kinds and molecular weights of non-ionic compounds used for evaluationof physical properties are shown in Table 34. TABLE 34 Kinds andmolecular weights (g/mol) of non-ionic compound Synthesis SynthesisSynthesis Compound Example Example 21 Example 23 Molecular weight 229259 288

Glass used in the following experiment was immersed in a cleaningsolution (KOH+IPA+water) for 4 hours or more, and washed with distilledwater and acetone and then dried to use. For evaluation, deionized waterwas used.

Changes in physical properties of the anionic surfactant were measuredfor changes in Krafft point, initial foamability, foam stability,stability to hard water, surface tension, etc.

3-2-1. Measurement of Physical Properties of Non-Ionic Compound

1) Conditions of Measuring Sample

The non-ionic compounds of Synthesis Examples 19, 21, and 23 wererespectively dissolved in 99 g of water to prepare samples of 1 wt %concentration to use for measurement. All the samples showed transparentphases.

2) Measurement of Krafft Point of Non-Ionic Compound

While cooling transparent non-ionic compound solutions of SynthesisExamples 19, 21, and 23, temperatures when the solutions became cloudywere measured (condition when lowering temperature). Also, whileelevating the temperature of the clouded solution, temperatures when thesolutions became transparent again were measured (condition whenelevating temperature).

SLS showed cloudiness at 2-3° C. under a condition of loweringemperature, and became transparent again at 14° C. under a condition ofelevating temperature. Meanwhile, Synthesis Examples 19, 21, and 23 ofthe present invention did not show cloudiness to 0° C. under loweringtemperature drop conditions. In cases where cloudiness did not occur at0° C., experiments under the elevation temperature condition were notconducted.

3) Measurement of Foaming Property (Initial Foamability and FoamStability)

Foamabilities of Synthesis Examples 19, 21, and 23 were measured using asemi-micro TK method, and the results are shown in Table 35. Experimentswere repeated three times, and a mean value was taken. For theexperiment, a 1% aqueous solution was used. TABLE 35 (ml) 0 min. 1 min.2 min. 3 min. 4 min. 5 min. Synthesis 210 55 — — — — Example Synthesis230 228 228 225 223 223 Example Synthesis — — — — — — Example

As shown in Table 35, Synthesis Example 21 showed a significant level ofinitial foamability and foam stability, while Synthesis Example 19produced foam at a comparatively superior level but the foam immediatelydisappeared to show low stability in foam. Synthesis Example 23 did notproduce foam. From these results, it is considered that SynthesisExamples 19 and 23 can be applied for a low-foaming laundry detergent,etc. requiring that produced foam should immediately be broken, andSynthesis Example 21 can be applied for a dish washing detergentrequiring superior foaming property.

4) Measurement of Surface Tension

Surface tensions of non-ionic compounds of Synthesis Examples 19, 21,and 23 were measured using a tensiometer k12 from the Kruss Company witha ring method. The non-ionic compound samples of Synthesis Examples 19,21, and 23 were prepared in solutions of concentrations of 1%, 0.1%,0.01%, and 0.001% by weight to use for the experiment. The results areshown in Table 36. TABLE 36 Results of measuring surface tension ofnon-ionic compound (unit: mN/m) Concentration 1% 0.1% 0.01% 0.001%Synthesis Example 31.94 29.59 31.67 53.88 Synthesis Example 28.87 28.3626.30 50.34 Synthesis Example 46.51 56.46 64.05 —

As shown in Table 36, Synthesis Examples 19 and 21 showed comparativelylow surface tensions in the measuring sample concentration range, butSynthesis Example 23 showed a high surface tension.

5) Measurement of Stability to Hard Water.

Hard water at a 10,000 ppm concentration prepared by dissolving 11.69 gof CaCl2.2H₂O in 1 L of water was used for the experiments. For thenon-ionic compounds of Synthesis Examples 19, 21, and 23, 100 ml of eachsample of concentration of 0.5% (weight ratio) were used to evaluatestability to hard water by adding hard water until pearl is appear. Thetests were repeated by three times, and a mean value was measured. Asresults, since each non-ionic compound had a small negative charge, anyof them was not precipitated.

3-2-2. Measurement of Changes in Physical Properties of SLS in a MixedSystem of Anionic Surfactant (SLS) and Non-Ionic Compound of SynthesisExample 19

Examples 38 to 43

Sample solutions were prepared with mole ratios of the anionicsurfactant (SLS) and the non-ionic compound of Synthesis Example 19 asshown in Table 39, and all the prepared sample solutions weretransparent. Cationic surfactant, quaternary ammonium salt, was added sothat its mole ratio for SLS became 1:0.001 TABLE 37 Samples formeasuring mixed system Example Example 38 Example

Example

Example

Example

Example 43 SLS/Non-ion 0.56/0.44 0.63/0.37 0.72/0.28 0.83/0.17 0.93/0.070.993/0.007 Phase stability transparent transparent transparenttransparent transparent Transparent[Experiment 6]Measurement of Physical Properties of Examples 38 to 431) Measurement of Krafft Point

Krafft points of Examples 38 to 43 (mixed systems of SLS and non-ioniccompound) were measured, and the results are shown in Table 38. TABLE 38Measurement of Krafft point of mixed system (unit ° C.) Example 38Example 39 Example 40 Example 41 Example 42 Example 43 When dropping 0<0< 0< 0< 0 2˜3 When elevating — — — — 19 19˜20 temperature

As shown in Table 38, Examples 38 to 41 with a mixing ratio of thenon-ionic additive of 1/0.25 or more showed decreased Krafft points to0° C. or less. Examples 38 to 41 showed stable phases even at a lowtemperature, compared to SLS alone. In addition, the solutions ofExamples 42 and 43 became opaque at 0˜3° C. under the loweringtemperature, and they became transparent again at 19° C. under theelevation temperature.

2) Measurement of Foaming Property (Initial Foamability and FoamStability)

Foaming propertys of Examples 38 to 43 were measured, and the resultsare shown in Table 39. TABLE 39 Results of measuring foaming property ofmixed system (unit: ml) 0 min. 1 min. 2 min. 3 min. 4 min. 5 min.Example 38 200 200 200 200 200 200 Example 39 248 245 245 245 245 245Example 40 245 245 245 245 245 245 Example 41 245 245 245 245 245 245Example 42 250 248 248 245 245 245 Example 43 250 250 250 250 250 250

As shown in Table 39, as the mixing ratio of the non-ionic compound islower, like Example 43, initial foamability and foam stability tended tobe similar to SLS. Also, although as the mixing ratio of the non-ionicadditive decreases, initial foamability increases, once the formed foamis significantly stably maintained, it shows superior foam stability.From these results, it is considered that these mixed systems can beapplied for products requiring sufficient foaming such as shampoo orbody cleanser, etc.

3) Measurement of Surface Tension

The results of measuring surface tension are show in Table 40. TABLE 40Results of measuring changes in surface tension of mixed system (roomtemperature) Concentration 1% 0.1% 0.01% 0.001% Example 38 26.13 23.3623.46 41.90 Example 39 26.10 23.34 23.56 43.33 Example 40 26.56 23.5123.80 46.79 Example 41 27.13 23.33 26.26 48.25 Example 42 28.37 23.1129.02 52.65 Example 43 31.06 24.05 34.05 60.81

As shown in Table 40, Example 43 showed a surface tension value almostthe same as SLS, but as the mixing ratio of the non-ionic compoundincreased, the surface tension value tended to decrease. The resultsthat surface tension decreases and is maintained constantly at a lowconcentration mean that the cmc is low, which indicates that even asmall amount can show superior cleaning power.

4) Measurement of Change in Stability to Hard Water for Mixed System

Results of measuring stability to hard water for mixed system are shownin Table 41. TABLE 41 Measurement of change in stability to hard waterfor mixed system Example 38 Example 39 Example 40 Example 41 Example 42Example 43 1^(st) 6.10 6.70 6.55 3.60 2.90 3.15 2^(nd) 6.10 6.60 7.205.15 2.95 3.35 Mean 6.10 6.65 6.88 4.38 2.93 3.25 Hard water 575 624 644420 285 315 concentration (ppm)

As shown in Table 41, as the mixing ratio of the non-ionic compoundincreased, the added amount of hard water increased. The mixed system ofthe SLS and the non-ionic compound showed stability to hard watersuperior by about twice compared to SLS alone.

3-2-3. Measurement of Changes in Physical Properties of SLS in a MixedSystem of SLS and Non-Ionic Compound of Synthesis Example 23.

Examples 44 to 49

Sample solutions were prepared with mole ratios of the anionicsurfactant (SLS) and the non-ionic compound of Synthesis Example 23 asshown in Table 35, and all the prepared solutions were transparent.Cationic surfactant quaternary ammonium salt was added so that its moleratio for SLS became 1:0.001. TABLE 42 Samples for measuring mixedsystem Example Example 44 Example 45 Example 46 Example 47 Example 48Example 49 SLS/Non-ion 0.67/0.33 0.73/0.27 0.8/0.2 0.89/0.11 0.95/0.050.995/0.005 Phase stability transparent transparent transparenttransparent transparent Transparent[Experiment 7]Measurement of Physical Properties of Examples 44 to 491) Measurement of Krafft Point

Krafft point of a mixed system of the SLS and the non-ionic compound wasmeasured, and the results are shown in Table 43. TABLE 43 Measurement ofKrafft point of mixed system (unit ° C.) Example Example 44 Example 45Example 46 Example 47 Example 48 Example 49 When dropping 0< 0< 0< 0< 01 When elevating — — — — 11˜12 13 temperature

As shown in Table 43, Examples 44 to 47 with mixing ratios of thenon-ionic additive of 1/0.25 or more showed decreased Krafft points to0° C. or lower. The solutions of Examples 48 and 49 became opaque at0˜1° C. under the lowering temperature, and they became transparentagain at 11˜13° C. under the elevation temperature. It can be seen thatthis mixed system has stability to low temperature superior to SLS.

2) Measurement of Foaming Property (Initial Foamability and FoamStability)

Results of measuring foaming property of Examples 44 to 49 are shown inTable 44. TABLE 44 Results of measuring foaming stabilty of mixed system(unit: ml) 0 min. 1 min. 2 min. 3 min. 4 min. 5 min. Example 44 183 160143 125 113 105 Example 45 190 160 153 145 145 138 Example 46 200 190183 178 175 173 Example 47 200 200 198 195 195 195 Example 48 223 218213 210 203 198 Example 49 233 228 228 225 225 223

As shown in Table 44, as the mixing ratio of the non-ionic compoundbecame lower, initial foamability and foam stability tended to besimilar to SLS. Also, as the mixing ratio of the non-ionic compounddecreased, the initial foamability increased and the foam graduallydecreased as time passed. Such physical properties can be applied for adish washig detergent or laundry detergent requiring superior rinsing.

3) Measurement of Surface Tension

Results of measuring surface tension are shown in Table 45. TABLE 45Results of measuring change in surface tension of mixed system (roomtemperature) Concentration 1% 0.1% 0.01% 0.001% Example 44 34.31 31.6439.67 61.51 Example 45 35.15 31.72 39.08 60.73 Example 46 33.74 32.1641.13 61.68 Example 47 36.18 32.17 43.40 62.94 Example 48 36.55 31.8747.51 64.63 Example 49 37.07 33.48 56.61 64.20

As shown in Table 45, Examples 48 and 49 showed surface tension valuesalmost the same as SLS, but as the mixing ratio of the non-ioniccompound increased, the surface tension decreased. The results thatsurface tension decreases and is maintained constantly even at a lowerconcentration means that the cmc is low, which indicates that even withonly a small amount can show superior effects to cleaning.

4) Measurement of Stability to Hard Water for Mixed System

Results of measuring stability to hard water for a mixed system areshown in Table 46. TABLE 46 Measurement of change in stability to hardwater for mixed system Concentration 1% 0.1% 0.01% 0.001% Example 4434.31 31.64 39.67 61.51 Example 45 35.15 31.72 39.08 60.73 Example 4633.74 32.16 41.13 61.68 Example 47 36.18 32.17 43.40 62.94 Example 4836.55 31.87 47.51 64.63 Example 49 37.07 33.48 56.61 64.20

As results, as the mixing ratio of non-ionic compound increased,stability to hard water increased by about twice as much.

As explained, the mixed surfactant system of the present inventioncomprises a compound comprising at least one kind of non-ionic group orcationic group to increase cleaning power of an anionic surfactant,control initial foamability and foam stability, and increase stabilityto hard water and lower surface tension and cmc, and thus it is veryeffective for solid, liquid, gel, and paste types detergents, etc. suchas laundry detergent, shampoo, rinse, dish washing detergent, hair-dye,fabric softener, soap, etc.

1. A surfactant system comprising a) an anionic surfactant; b) acationic compound represented by the following Chemical Formula 1; andc) a non-ionic surfactant:

(wherein R₁, R₂, R₃, and R₄ are independently or simultaneously C1˜C20saturated or unsaturated chain groups, benzyl groups, hydroxy ethylgroups, or hydroxy ethyl groups to which 1 to 20 ethylene oxide orpropylene oxide groups are attached; and X is a halogen atom, a sulfategroup, or an acetate group).
 2. The surfactant system according to claim1, wherein the mixing ratio of the a) anionic surfactant, the b)cationic compound, and the c) non-ionic surfactant is1:0.001:0.001˜1:1:1 by mole ratio.
 3. The surfactant system according toclaim 1, wherein the cationic compound is prepared by a processcomprising the step of heat-reacting a tertiary amine with an alkylhalide under an alkaline condition to cause quaternarization.
 4. Asurfactant system comprising a) an anionic surfactant; and b) a cationiccompound represented by the following Chemical Formula 2:

(wherein R₁, R₂, R₃, and R₅ are independently or simultaneously C1˜C20saturated or unsaturated chain groups, benzyl groups, hydroxy ethylgroups, or hydroxy ethyl groups to which 1 to 20 ethylene oxide orpropylene oxide groups are attached; R₄ is a C1˜C20 alkyl group, analkyl group to which 1 to 10 ethylene oxide or propylene oxide groupsare attached, or an alkyl group to which 1 or more hydroxyl groups arebound; n is an integer of 1 to 20; and X is a halogen atom, a sulfategroup, or an acetate group.)
 5. The surfactant system according to claim4, wherein the mixing ratio of the a) anionic surfactant and the b)cationic compound is 1:0.0001˜1:0.5 by mole ratio.
 6. The surfactantsystem according to claim 4, wherein the cationic compound is selectedfrom a group consisting of 1,6-[2-(N-dimethylamino)ethanol]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol]hexane,1,6-[2-(N,N-butylmethylamino)ethanol]hexane,1,6-[2-(N,N-methyloctylamino)ethanol]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol]hexane,1,8-[2-(N-dimethylamino)ethanol]octane,1,8-[2-(N,N-ethylmethylamino)ethanol]octane,1,8-[2-(N,N-butylmethylamino)ethanol]octane,1,8-[2-(N,N-methyloctylamino)ethanol]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol]octane,1,6-[2-(N-dimethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₂hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(EO)₂]octane,1,7-[2-(N,N-ethylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(EO)₂] octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N-dimethylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-butylmethylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]octane,1,6-[2-(N-dimethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N-dimethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N-dimethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]octane, and a mixturethereof.
 7. The surfactant system according to claim 4, wherein thecationic compound comprises one or more kinds of quaternary ammoniumsalts comprising one or more kinds of hydroxy ethyl groups in amolecule, and one or more kinds of quaternary ammonium salts comprisinga functional group in which 2 to 10 moles of ethylene oxide (EO) orpropylene oxide (PO) groups are added to the hydroxyl group.
 8. Thesurfactant system according to claim 4, wherein the cationic compound isprepared by a process comprising the steps of i) reacting a secondaryamine with an alkyl halide under an alkaline condition to prepare atertiary amine; and ii) binding a linker represented by the followingChemical Formula 3 to the tertiary amine obtained in step i) to causequaternarization:X+CH₂)n-X  [Chemical Formula 3] (wherein n is an integer of 1 to 20; andX is a halogen atom, a sulfate group, or an acetate group.).
 9. Thesurfactant system according to claim 8, wherein the cationic compound isprepared by a process comprising the steps of i) binding the linker ofChemical Formula 3 with a secondary amine under an alkaline condition toprepare a tertiary amine; and ii) binding an alkyl halide to thetertiary amine obtained in step i) to cause quaternarization.
 10. Thesurfactant system according to claim 1, wherein the anionic surfactantis selected from a group consisting of sodium lauryl sulfonate (SLS),sodium lauryl ether sulfonate (SLES), a linear alkyl benzene sulfonate(LAS), monoalkyl phosphate (MAP), acyl isethionate (SCI), an alkylglyceryl ether sulfonate (AGES), acylglutamate, acyltaurate, a fattyacid metal salt, and a mixture thereof.
 11. The surfactant systemaccording to claim 1, wherein the non-ionic surfactant is selected froma group consisting of an ethoxylated fatty alcohol, an ethoxylated fattyacid, an ethoxylated alkyl phenol, an alkanolamide (fatty acidalkanolamide), an ethoxylated fatty acid alkanolamide, a fatty amineoxide, a fatty amido amine oxide, a glyceryl fatty acid ester, sorbitan,an ethoxylated sorbitan ester, an alkyl poly glycoside, anethylene/propylene oxide copolymer, an ethoxylated-propoxylated fattyalcohol, and a mixture thereof.
 12. A surfactant system comprising a) ananionic surfactant; and b) a compound represented by the followingChemical Formula 4:

(wherein R₁, R₂, R₃, and R₄ are independently or simultaneously C1˜20saturated or unsaturated chain groups, benzyl groups, hydroxy ethylgroups, or hydroxy ethyl groups to which 1 to 20 ethylene oxide orpropylene oxide groups are added; R₅ is a C1˜20 alkyl group, an alkylgroup to which 1 to 20 ethylene oxide or propylene oxide groups areadded, an alkyl group to which one or more hydroxyl groups are bound, analkyl group comprising at least one double bond, or an alkyl groupcomprising at least one ether group; A₁ and A₂ are independently orsimultaneously C1˜20 saturated or unsaturated chain groups, benzylgroups, hydroxy ethyl groups, hydroxy ethyl groups to which 1 to 20ethylene oxide or propylene oxide groups are added, or oxygen anions(O—); n is an integer of 0 to 20; X is a halogen atom, a sulfate group,a methyl sulfate group, or an acetate group.).
 13. The surfactant systemaccording to claim 12, wherein the mixing ratio of the a) anionicsurfactant and the b) compound of Chemical Formula 4 is 1:0.0001˜1:1.0by mole ratio.
 14. A surfactant system comprising a) an anionicsurfactant; b) a compound represented by the following Chemical Formula4; and c) a non-ionic surfactant, a cationic surfactant or a mixturethereof:

(wherein R₁, R₂, R₃, and R₄ are independently or simultaneously C1˜20saturated or unsaturated chain groups, benzyl groups, hydroxy ethylgroups, or hydroxy ethyl groups to which 1 to 20 ethylene oxide orpropylene oxide groups are added; R₅ is a C1˜20 alkyl group, an alkylgroup to which 1 to 20 ethylene oxide or propylene oxide groups areadded, an alkyl group to which one or more hydroxyl groups are bound, analkyl group comprising at least one double bond, or an alkyl groupcomprising at least one ether group; A₁ and A₂ are independently orsimultaneously C1˜20 saturated or unsaturated chain groups, benzylgroups, hydroxy ethyl groups, hydroxy ethyl groups to which 1 to 20ethylene oxide or propylene oxide groups are added, or oxygen anions(O—); n is an integer of 0 to 20; and X is a halogen atom, a sulfategroup, a methylsulfate group, or an acetate group.).
 15. The surfactantsystem according to claim 14, wherein the mixing ratio of the a) anionicsurfactant, the b) compound of Chemical Formula 4 and the c) non-ionicsurfactant is 1:0.0001:0.000 1˜1:1.0:0.5 by mole ratio.
 16. Thesurfactant system according to claim 14, wherein the mixing ratio of thea) anionic surfactant, the b) compound of Chemical Formula 4, and the c)cationic surfactant is 1:0.0001:0.0001˜1:1.0:0.5.
 17. The surfactantsystem according to claim 14, wherein the mixing ratio of the a) anionicsurfactant, the b) compound of Chemical Formula 4, and the c) mixture ofnon-ionic surfactant and cationic surfactant is1:0.0001:0.0001˜1:1.0:0.5.
 18. The surfactant system according to claim12, wherein the compound of Chemical Formula 4 is a non-ionic compoundselected from a group consisting of N,N,N-dimethyllauryl amine oxide;N,N,N-ethylmethyllauryl amine oxide; N,N,N-dimethyldodecyl amine oxide;N,N,N-butylmethyllauryl amine oxide; N,N,N-dimethylhexadecyl amineoxide; N,N,N-dibutyllauryl amine oxide;N,N,N-(2-hydroxyethyllaurylmethyl)amine oxide;N,N,N-(di-2-hydroxyethyllauryl)amine oxide;N,N,N-(2-hydroxyethyllaurylbutyl)amine oxide;N,N,N-(2-hydroxy(EO)₅ethyllaurylmethyl)amine oxide;N,N,N-(2-hydroxyethyl(PO)₅ 1 aurylmethyl)amine oxide;N,N,N-(2-hydroxyethyl(EO)₅(PO)₅laurylmethyl)amine oxide;N,N,N-(2-hydrxoyethyl(EO)₁₀laurylmethyl)amine oxide;N,N,N-(2-hydrxoyethyl(EO)₁₅laurylmethyl)amine oxide;1,6-(N,N-butylmethylaminooctyl)hexane;1,6-(N,N-butylmethylaminooctyl)dipropylether;1,6-(N,N-butylmethylaminooctyl)-3-hydroxyhexane;1,6-(N,N-butylmethylaminooctyl) butane; 1,6-(N,N-butylmethylaminooctyl)octane; 1,6-(N,N-butylmethyl amin oxyl)-2-hydroxypropane;1,6-[2-(N-methylaminooctyl)ethanol]hexane;1,6-[2-(N-methylaminooctyl)ethanol(EO)₅]hexane;1,6-[2-(N-methylaminooctyl)ethanol(PO)₅]hexane;1,6-[2-(N-methylaminooctyl)ethanol(EO)₅(PO)₅]hexane;1,6-[2-(N-methylaminooctyl)ethanol (EO)₁₀]hexane;1,6-[2-(N-methylaminooctyl)ethanol]dipropylether;1,6-[2-(N-methylaminooctyl)ethanol]-2-hydroxypropane;1,6-[2-(N-methylaminooctyl)Ethanol]butane;1,6-[2-(N-methylaminooctyl)ethanol]octane; and a mixture thereof. 19.The surfactant system according to claim 18, wherein the non-ioniccompound is prepared by reacting a tertiary amine with peroxide.
 20. Thesurfactant system according to claim 18, wherein the non-ionic compoundis prepared by binding a linker represented by the following ChemicalFormula 5 to a secondary amine to obtain a tertiary amine, and thenreacting the tertiary amine with hydrogen peroxide:

(wherein n is an integer of 1 to 20; X is a halogen atom; and R₅ ishydrogen or an alkyl or allyl group comprising at least one double bond,a hydroxyl group, or an ether group.).
 21. The surfactant systemaccording to claim 12, wherein the compound of Chemical Formula 4 is acationic compound selected from a group consisting ofdimethyloctylethoxy ammonium, dimethyl decyl ethoxy ammonium, dimethyllauryl ethoxy ammonium, dimethyloctylethanol (EO)₅ ammonium,dimethyldecylethanol (EO)₅ ammonium, dimethyllaurylethanol (EO)₅ammonium, dimethyloctylethanol (EO)₁₀ ammonium, dimethyldecylethanol(EO)₁₀ ammonium, dimethyllaurylethanol (EO)₁₀ ammonium,dimethyloctylethanol (EO)₁₅ ammonium, dimethyldecylethanol (EO)₁₅ammonium, dimethyllaurylethanol(EO)₁₅ ammonium, trimethyloctyl ammonium,tridecyllauryl ammonium, trimethyllauryl ammonium,1,6-[2-(N-dimethylamino)ethanol]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol]hexane,1,6-[2-(N,N-butylmethylamino)ethanol]hexane,1,6-[2-(N,N-methyloctylamino)ethanol]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol]hexane,1,8-[2-(N-dimethylamino)ethanol]octane,1,8-[2-(N,N-ethylmethylamino)ethanol]octane,1,8-[2-(N,N-butylmethylamino)ethanol]octane,1,8-[2-(N,N-methyloctylamino)ethanol]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol]octane,1,6-[2-(N,-dimethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane,1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₄]octane,1,8-[p2-(N,N-butylmethylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]octane,1,6-[2-(N-dimethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N-dimethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N-dimethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]octane, and a mixturethereof.
 22. The surfactant system according to claim 21, wherein thecationic compound is prepared by a process comprising the steps of i)reacting a secondary amine with a compound represented by the followingChemical Formula 5 under an alkaline condition to prepare a tertiaryamine; and ii) binding the tertiary amine with a compound comprising aC1˜20 saturated or unsaturated chain group, a benzyl group, a hydroxyethyl group, or a hydroxy ethyl group to which 1 to 20 ethylene oxide orpropylene oxide groups are added to cause quaternarization:

(wherein n is an integer of 1 to 20; X is a halogen atom; R₅ ishydrogen, or an alkyl or allyl group comprising at least one doublebond, a hydroxyl group, or an ether group).
 23. The surfactant systemaccording to claim 21, wherein the cationic compound is prepared by aprocess comprising the steps of i) binding a compound comprising C1˜20saturated or unsaturated chain groups, benzyl groups, hydroxy ethylgroups, or hydroxy ethyl groups to which 1 to 20 ethylene oxide orpropylene oxide groups are added to a secondary amine to prepare atertiary amine; and ii) binding the tertiary amine with the compound ofChemical Formula 4 to cause quaternarization.
 24. The surfactant systemaccording to claim 12, wherein the anionic surfactant is selected from agroup consisting of sodium lauryl sulfonate (SLS), sodium lauryl ethersulfonate (SLES), a linear alkyl benzene sulfonate (LAS), monoalkylphosphate (MAP), acyl isethionate (SCI), an alkyl glyceryl ethersulfonate (AGES), acylglutamate, acyltaurate, a fatty acid metal salt,and a mixture thereof.
 25. The surfactant system according to claim 14,wherein the non-ionic surfactant is selected from a group consisting ofalcohol alkoxylate, alkylphenol ethoxylate, alkylpolyglycosides, amineoxide, alkanolamide, and a mixture thereof.
 26. The surfactant systemaccording to claim 14, wherein the cationic surfactant is selected froma group consisting of a compound of an amine salt form, a compoundcomprising quaternary ammonium, a monoalkyl dimethyl amine derivative, adialkyl monomethyl amine derivative, an imidazoline derivative, aquaternary ammonium compound of a Geminic form, a cationic surfactant ofan oligomeric quaternary ammonium form, and a mixture thereof.
 27. Adetergent composition of solid, liquid, gel, or paste types comprisingthe surfactant system of claim
 1. 28. A detergent composition of solid,liquid, gel, or paste types comprising the surfactant system of claim 4.29. A detergent composition of solid, liquid, gel, or paste typescomprising the surfactant system of claim
 12. 30. The surfactant systemaccording to claim 4, wherein the anionic surfactant is selected from agroup consisting of sodium lauryl sulfonate (SLS), sodium lauryl ethersulfonate (SLES), a linear alkyl benzene sulfonate (LAS), monoalkylphosphate (MAP), acyl isethionate (SCI), an alkyl glyceryl ethersulfonate (AGES), acylglutamate, acyltaurate, a fatty acid metal salt,and a mixture thereof.
 31. The surfactant system according to claim 14,wherein the compound of Chemical Formula 4 is a non-ionic compoundselected from a group consisting of N,N,N-dimethyllauryl amine oxide;N,N,N-ethylmethyllauryl amine oxide; N,N,N-dimethyldodecyl amine oxide;N,N,N-butylmethyllauryl amine oxide; N,N,N-dimethylhexadecyl amineoxide; N,N,N-dibutyllauryl amine oxide;N,N,N-(2-hydroxyethyllaurylmethyl)amine oxide;N,N,N-(di-2-hydroxyethyllauryl)amine oxide;N,N,N-(2-hydroxyethyllaurylbutyl)amine oxide;N,N,N-(2-hydroxy(EO)₅ethyllaurylmethyl)amine oxide;N,N,N-(2-hydroxyethyl(PO)₅laurylmethyl)amine oxide;N,N,N-(2-hydroxyethyl(EO)₅(PO)₅laurylmethyl)amine oxide;N,N,N-(2-hydrxoyethyl(EO)₁₀laurylmethyl)amine oxide;N,N,N-(2-hydrxoyethyl(EO)₁₅laurylmethyl)amine oxide;1,6-(N,N-butylmethylaminooctyl)hexane;1,6-(N,N-butylmethylaminooctyl)dipropylether;1,6-(N,N-butylmethylaminooctyl)-3-hydroxyhexane;1,6-(N,N-butylmethylaminooctyl) butane; 1,6-(N,N-butylmethylaminooctyl)octane; 1,6-(N,N-butylmethyl amin oxyl)-2-hydroxypropane;1,6-[2-(N-methylaminooctyl)ethanol]hexane;1,6-[2-(N-methylaminooctyl)ethanol(EO)₅]hexane;1,6-[2-(N-methylaminooctyl)ethanol(PO)₅]hexane;1,6-[2-(N-methylaminooctyl)ethanol(EO)₅(PO)₅]hexane;1,6-[2-(N-methylaminooctyl)ethanol (EO)₁₀]hexane;1,6-[2-(N-methylaminooctyl)ethanol]dipropylether;1,6-[2-(N-methylaminooctyl)ethanol]-2-hydroxypropane;1,6-[2-(N-methylaminooctyl)Ethanol]butane;1,6-[2-(N-methylaminooctyl)ethanol]octane; and a mixture thereof. 32.The surfactant system according to claim 14, wherein the compound ofChemical Formula 4 is a cationic compound selected from a groupconsisting of dimethyloctylethoxy ammonium, dimethyl decyl ethoxyammonium, dimethyl lauryl ethoxy ammonium, dimethyloctylethanol (EO)₅ammonium, dimethyldecylethanol (EO)₅ ammonium, dimethyllaurylethanol(EO)₅ ammonium, dimethyloctylethanol (EO)₁₀ ammonium,dimethyldecylethanol (EO)₁₀ ammonium, dimethyllaurylethanol (EO)₁₀ammonium, dimethyloctylethanol (EO)₁₅ ammonium, dimethyldecylethanol(EO)₁₅ ammonium, dimethyllaurylethanol(EO)₁₅ ammonium, trimethyloctylammonium, tridecyllauryl ammonium, trimethyllauryl ammonium,1,6-[2-(N-dimethylamino)ethanol]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol]hexane,1,6-[2-(N,N-butylmethylamino)ethanol]hexane,1,6-[2-(N,N-methyloctylamino)ethanol]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol]hexane,1,8-[2-(N-dimethylamino)ethanol]octane,1,8-[2-(N,N-ethylmethylamino)ethanol]octane,1,8-[2-(N,N-butylmethylamino)ethanol]octane,1,8-[2-(N,N-methyloctylamino)ethanol]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol]octane,1,6-[2-(N,-dimethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₂]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₂]hexane,1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane,1,6-[2-(N-dimethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(EO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₂]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(EO)₄]octane,1,8-[p2-(N,N-butylmethylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(EO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(EO)₄]octane,1,6-[2-(N-dimethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₂]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]hexane,1,6-[2-(N-dimethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-ethylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-butylmethylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-methyloctylamino)ethanol(PO)₄]hexane,1,6-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]hexane,1,8-[2-(N-dimethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₂]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₂]octane,1,8-[2-(N-dimethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-ethylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-butylmethylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-methyloctylamino)ethanol(PO)₄]octane,1,8-[2-(N,N-dodecylmethylamino)ethanol(PO)₄]octane, and a mixturethereof.
 33. The surfactant system according to claim 14, wherein theanionic surfactant is selected from a group consisting of sodium laurylsulfonate (SLS), sodium lauryl ether sulfonate (SLES), a linear alkylbenzene sulfonate (LAS), monoalkyl phosphate (MAP), acyl isethionate(SCI), an alkyl glyceryl ether sulfonate (AGES), acylglutamate,acyltaurate, a fatty acid metal salt, and a mixture thereof.
 34. Adetergent composition of solid, liquid, gel, or paste types comprisingthe surfactant system of claim 14.